Multifunctional foaming composition with wettability modifying, corrosion inhibitory and mineral scale inhibitory/dispersants properties for high temperature and ultra high salinity

ABSTRACT

The present invention is related to the obtaining and using of multifunctional foaming compositions with wettability modifying, corrosion inhibitory and inhibitory/dispersants mineral scale properties with high stability in environments of high temperature, high pressure and tolerance to high concentrations of divalent ions such as calcium, magnesium, strontium and barium. The multifunctional foaming compositions are obtained from the combination of supramolecular complexes resulting from interactions of alkyl amido propyl hydroxysultaines and/or alkyl amido propyl betaines and/or alkyl hydroxysultaines and/or alkyl betaines and anionic surfactant of type alkyl hydroxyl sodium sulfonate and alkenyl sulphonates of sodium, with cationic surfactants as tetra-alkyl ammonium halides and copolymers derivatives of itaconic acid/sodium vinyl sulfonate and/or terpolymers derived from itaconic acid/sodium vinyl sulphonate/aconitic acid. These multinational foaming compositions control the gas channeling and favorably change the wettability and increase the recovery factor of crude oil in naturally fractured reservoirs of carbonate type and heterogeneous lithology. In addition to this, the multifunctional foaming compositions of this invention exhibit anti-corrosive properties in typical environments of production tubing of crude oil and antifouling/dispersants of mineral salts as calcium carbonate, calcium sulfate, barium and strontium in the reservoir and in the production and injection pipelines.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This claims priority to Mexican Patent Application No. MX/a/2014/013981,filed on Nov. 18, 2014, the entire contents of which are fullyincorporated herein by reference.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to the obtaining and use ofmultifunctional foaming compositions having wettability modifying,corrosion inhibitory and mineral scale inhibitory/dispersant properties,that exhibit high stability and high performance under conditions thatinvolving ultra-high salinity brines, high temperature and highpressure, and have application in the control of the canalization offluids in naturally fractured reservoirs of heterogeneous lithology,increase the production of crude oil due to changing the rockwettability favorably in enhanced recovery processes under conditions ofhigh temperature and ultra-high salinity, as well as control uniform andlocalized corrosion problems that occur in production rigs of crude oilunder conditions of high temperature and ultra-high salinity, inhibitand dispersed mineral scale as calcium carbonate, sulfates of calcium,barium and strontium, formed upon contact the injection water with theformation water present in the oil field and for their application canbe used seawater and/or connate water feature of the reservoir todissolve the multifunctional foaming composition.

The multifunctional foaming compositions of the present invention areobtained from the combination of supramolecular complexes resulting frominteractions of alkyl amido propyl hydroxysultaines and/or alkyl amidopropyl betaines and/or alkyl hydroxysultaines and/or alkyl betaines andanionic surfactants as alkyl hydroxy sodium sulphonates and alkenylsodium sulphonates, with cationic surfactants as tetra-alkyl ammoniumhalides and copolymers derived of itaconic acid/sodium vinyl sulfonateand/or terpolymers derived from itaconic acid/sodium vinylsulphonate/aconitic acid.

BACKGROUND OF THE INVENTION

One of the major technological challenges that currently exist worldwidein naturally fractured carbonate reservoirs (NFCR) than they presenthigh temperature and high salinity conditions; it is to increase the oilrecovery factor through the use of chemicals. The NFCR are characterizedby possessing low porosities, present areas of preferential flow, thisdue to the existence of fractures and dissolution cavities and exhibitwettability to the oil or intermediate; therefore, chemicals that areused in the same, in order to increase the recovery factor, must bepossess the ability to control the channeling of fluid and alter therock wettability of oil-wet to water-wet. Added to this, if in the NFCRconditions of high temperature and salinity, and problems ofincompatibility between the injection water and formation water, it isnecessary that the chemicals that are used in enhanced oil recoveryprocesses, be tolerant to high salinity and concentrations of divalentions, control problems of formation damage caused by mineral salt scaleand problems of uniform corrosion as well as scales in the productionrigs.

Traditionally, the way to control channeling of fluids in NFCR has beenthrough the use of foaming agents and/or gels [SPE 145718, 2011,Development of a new foam EOR model from laboratory and field data ofthe naturally fractured Cantarell Field; SPE 130655, 2010,High-temperature conformance field application through coiled tubing asuccessful case history; SPE 129840, 2010, Application of gas formobility control in chemical EOR in problematic carbonate reservoirs andthe performance thereof, is a function of reservoir temperature,salinity and concentration of divalent ions that are present in waterinjection and/or in the formation water and the type of crude oil whichare present in the reservoir. Also, the benefits of use foaming agentswith wettability modifying properties that control gas channelingproblems and increase the recovery factor in NFCR that not presentincompatibility of waters problems has been recently demonstrated inMexico [AIPM, 13-33, 2012, Control de movilidad del gas en el casqueteen pozos del campo Akal perteneciente al Complejo Cantarell; SPE 145718,2011, Development of a new foam EOR model from laboratory and field dataof the naturally fractured Cantarell Field]. Additionally, the foamingagents are commonly used in various stages of the exploitation of oilfields as: drilling and fracturing; as well as in gas reservoirs andcondensates with water supply. In this type of gas and condensatereservoirs, the function of the foam is to maximize the gas productionthrough the weight reduction of the hydrostatic column generated byfluids (water, gas and condensate). Within the main chemical families ofsurfactants that have been used to generate foams and which haveapplication in enhanced oil recovery processes are: 1) Alkyl arylsulfonates (U.S. Pat. No. 5,273,682 “Viscosity control additives forfoaming mixture”); 2) Alkoxy alkyl benzenesulfonates (U.S. Pat. No.5,049,311 “Alkoxylated alkyl substituted phenol sulfonates compounds andcompositions, the preparation thereof and their use in variousapplications”); 3) Alpha olefin sulfonate (U.S. Pat. No. 4,607,695 “Highsweep efficiency steam drive oil recovery method”); 4) Alkyl amidobetaines (U.S. Pat. No. 7,104,327 “Methods of fracturing hightemperature subterranean zones and foamed fracturing fluids therefor”);5) Alkyl amido hydroxysultaines (U.S. Pat. No. 7,407,916 “Foamedtreatment fluids and associated methods”); and 6) Alkyl ether sulfates(Report DE-FC26-03NT15406 of the United States Department of Energy inAmerica Surfactant-Based Enhanced Oil Recovery Processes and FoamMobility Control). However, when in the reservoirs, the temperatureconditions are high (higher than 70° C.), the salinity is greater than30,000 ppm of total solids and the concentration of divalent ions, suchas, calcium and magnesium, it is more than 2,000 ppm, so that, thestability of the foam that are generated for this kind of chemicalsfamilies of surfactants decreases drastically. In order to increase thestability of the foam and thus its tolerance to high concentrations ofdivalent ions and/or temperature, they have been developed formulationsof foaming agents with improved properties as those listed below: TheU.S. Pat. No. 3,939,911 (Surfactant oil recovery process usable in hightemperature formations containing water having high concentrations ofpolyvalent ions) describes a system of three surfactants applied toprocesses of enhanced recovery in reservoirs of high temperature andwhose water formation contains of 200 to 14,000 ppm of polyvalent ionsdissolved, such as calcium or magnesium. The system of three surfactantsis made up of: 1) a water-soluble salt of an alkyl or alkylarylsulfonate, wherein the alkyl chain can be have from 5 to 25 carbonatoms, 2) a surfactant of phosphate ester with an average molecularweight which does not exceed 1000 UMA and 3) a sulfobetaine surfactantof the structural formula (1) wherein R is an alkyl group of 12 to 24carbon atoms. The combination is stable until at least a temperature of107° C. and resistant to attack by bacteria and inhibits scaleformation.

The U.S. Pat. No. 4,703,797 (Sweep improvement in enhanced oil recovery)mentions a method of improved swept during processes of enhanced oilrecovery. The method consists of generate a foam by the dispersion ofthe fluid displaced in an aqueous solution containing a surfactantformulation. The surfactant formulation consists of a foaming basedlignosulfonates and a foaming surfactant. Within the foaming surfactantsmention is made to the group consisting of anionic, nonionic andamphoteric surfactants. The U.S. Pat. No. 5,295,540 (Foam mixture forsteam and carbon dioxide drive oil recovery method) mentions a methodbased foams for the enhance the hydrocarbons production in subterraneanformations and consisting of: 1) inject vapor and fluids produced intothe formation and 2) injecting a vapor mixture, a non-condensable gasand an aqueous mixture of surfactant and polysaccharide. Within thesurfactants mentioned which can be used, they are find linear toluenesulfonates, alkylaryl sulfonates, dialkylaryl sulfonates, alpha olefinsulfonates and dimerized alpha olefin sulfonates. The U.S. Pat. No.5,542,474 (Foam mixture for carbon dioxide drive oil recovery method)mentions a method based foam to enhance the performance during the steamsupply or carbon dioxide into underground formations that containingcrude oil and which are formed by at least one producer well and oneinjector well. The sweep efficiency in the oil recovery process throughsteam supply is enhanced by: 1) inject steam until it starts to appearin the producer well and 2) then add to the forming a mixture of steam,not condensable gas and an aqueous solution of a polypeptide surfactant.The aqueous solution of surfactant-polypeptide forms a stable foam withthe oil of the formation at reservoir conditions. Within the surfactantsused as base of foaming agent are sodium salts and ammonium of sulfatedethoxylated alcohols, ethoxylated linear alcohols, linear toluenesulfonates. The U.S. Pat. No. 7,104,327 (Methods of fracturing hightemperature subterranean zones and foamed fracturing fluids therefor)provides methods for fracturing subterranean zones of high temperatureand aqueous fracturing fluids foamed and viscous for this purpose. Thefracturing fluid of the invention take in water, a terpolymer of2-acrylamido-2-methylpropane sulfonic acid, acrylamide and acrylic acidor salts thereof, a gas, a foaming agent and a breaker of viscosity forcontrolling and reduce the viscosity of the fracturing fluid. Thefoaming agent in this invention is selected from the group consisting ofC₈-C₂₂ alkylamido-betaine, alpha olefin sulfonate, chloride oftrimethyl-taloil-ammonium C₈-C₂₂ alquiletoxilado sulfate and chloride oftrimethyl-coco-ammonium; especially mention is made as foaming agent ofthe cocoamidopropyl betaine. The Mexican patent MX 297,297 (Composiciónespumante para alta temperatura y salinidad) is related to a foamingcomposition with enhanced that control the gas channeling in carbonatenaturally-fractured reservoirs with high-salinity and temperatureconditions through the synergistic effect resulting from thesupramolecular interaction of alpha olefin sulfonates of sodium withalkyl amido propyl betaines [structure (2)],

wherein R and R1 are independent alkyl chains linear or branched andwhose length varies from 1 to 30 carbon atoms.

The Mexican MX 297,297 and U.S. Pat. No. 8,722,588 patents, makesmention of supramolecular complexes resulting from alpha olefinsulfonates of sodium with alkyl amido propyl betaines interactions, canbe combined with anionic surfactants, preferably of the type3-hydroxy-alkyl sulfonate of sodium, with cationic surfactants of thetype quaternary salts of alkyl ammonium, preferably of the type chlorideor bromide of alkyl trimethyl ammonium, with sequestering of divalentions, preferably oligomers or copolymers derived from itaconic acid andwhose average molecular weight are in the range of 200 to 20,000Daltons, with gels derived from polymers or copolymers selected from ofthe polyacrylamides group, partially hydrolyzed polyacrylamide, xanthangum, poly (itaconic acid), poly (acrylic acid), poly(itaconic-co-acrylic-acid acid), poly (itaconates) and poly (acrylates).Also, in said patent it is indicated that the foaming compositions withenhanced stability possess applications in enhanced recovery processand/or production assurance. The patent makes no mention that thecompositions have application as wettability modifiers, corrosioninhibitors or antiscale; or that are present in the same copolymersderived from itaconic acid/vinyl sodium sulfonate and/or terpolymersderived from itaconic acid/sodium vinyl sulfonate/aconitic acid.

The Mexican patent application MX/a/2012/014187 (Composición espumantecon propiedades modificadoras de la mojabilidad e inhibitorias de lacorrosión para alta temperatura y ultra alta salinidad) is related tothe collection and use of foaming compositions withmodifying-wettability and corrosion-inhibitory properties thatcontrolling the channeling of fluids in naturally fractured carbonatereservoirs, alter the rock wettability favorably in processes forenhanced crude oil recovery and control uniform corrosion problems thatoccur in production rigs under high temperature and ultra-high salinityconditions; by the synergistic effect resulting from the supramolecularinteraction of alkyl amido propyl hydroxysultaines or alkylhydroxysultaines with alkyl hydroxysulfonates of sodium and alkenylsulphonates of sodium (FIG. 43). The foaming compositions withwettability modifying and corrosion inhibitory properties arecharacterized for being tolerant to high concentrations of divalent ionssuch as calcium, magnesium, strontium and barium and that for hisapplication to the reservoir can be used as transport media sea waterand/or congenital water characteristic of the reservoir. The patentapplication does not mention that the compositions have antiscaleproperties; or that, in the same are present cationic surfactants of thequaternary salts type of alkyl ammonium and/or copolymers derived fromitaconic acid/sodium vinyl sulfonate and/or terpolymers derivatives ofitaconic acid/sodium vinyl sulfonate/aconitic acid.

In the US patent application US 2007/0142235 A1 (Process for oilrecovery using surfactant gels) a composition and process for recoveringhydrocarbons are protected, this consist in inject an aqueous solutioninto a formation that containing hydrocarbon through one or moreinjection wells, displacing the solution into the formation andrecovering the hydrocarbon through one or more producer wells. Theaqueous solution contains one or more amphoteric surfactants of alkylamido betaines type [structure (4)] to form a viscoelastic surfactantgel that can be reduce the interfacial tension and increase theviscosity of the injection fluid simultaneously in some oils and brine.The viscoelastic gels are tolerant to electrolytes and multivalentcations and are particularly useful into reservoirs that have of mediumto high temperature, high salinity, high concentrations of divalent ionsand low porosity. Inside of the application are mentioned that thecomposition for recovering hydrocarbons containing one or moreamphoteric surfactants selected for their ability to low the interfacialtension and increase the viscosity simultaneously, in an aqueous medium,a secondary surfactant and optionally one or more polymers to provideviscosity residual. This patent application indicates that the secondarysurfactant can be selected from the anionic, cationic or nonionic groupand that the polymer that provides the residual viscosity is selectedfrom the group polyacrylamide, partially hydrolyzed polyacrylamide,xanthan gum, hydroxyethyl cellulose or guar gum. Also, the patentapplication mentions that the combination of alkyl amido betaines withsecondary surfactants of the linear type dodecyl benzene sodiumsulfonatesulfonate and arylalkyl xylene sodium sulfonate reduces theinterfacial tension and increases the viscosity of the system. Thepatent application does not mention that amphoteric surfactants are usedbased alkyl amido betaines and their mixtures for the foams generation,also it does not indicate that use mixtures of alkyl amido betaines andcationic surfactants of type quaternary salts of alkyl ammonium and/orcopolymers derived from the itaconic acid/vinyl sodium sulfonate and/orterpolymers derived from itaconic acid/sodium vinyl sulphonate/aconiticacid.

None of the aforementioned references it claims the development and useof multifunctional foaming compositions obtained from the combination ofsupramolecular complexes resulting from the interactions of alkyl amidopropyl hydroxysultaines and/or alkyl amido propyl betaines and/or alkylhydroxysultaines and/or alkyl betaines and anionic surfactants of typealkyl hydroxy sulphonates of sodium and/or alkenyl sulphonates ofsodium, with cationic surfactants of the type halide of tetra-alkylammonium and copolymers derived from itaconic acid/vinyl sodiumsulfonate and/or terpolymers derivatives of itaconic acid/sodium vinylsulfonate/aconitic acid. Such multifunctional compositions arecharacterized by having high stability in environments of hightemperature, high pressure and tolerance to high concentrations ofdivalent ions like calcium, magnesium, strontium and barium. It istherefore the object of the present invention to provide multifunctionalfoaming compositions with modifying wettability, uniform and localizedcorrosion inhibitory and inhibition/dispersion of mineral scales such ascalcium carbonate and sulfates of calcium, barium and strontium;composed of supramolecular complexes resulting from interactions ofalkyl amido propyl hydroxysultaines and/or alkyl amido propyl betainesand/or alkyl hydroxysultaines and/or alkyl betaines and anionicsurfactants of type alkyl hydroxy sulphonates of sodium and alkenylsulphonates of sodium, with cationic surfactants as tetra-alkyl ammoniumhalides and copolymers derived from itaconic acid/sodium vinyl sulfonateand/or terpolymers derived from itaconic acid/sodium vinylsulphonate/aconitic acid. The present invention has the advantage thatthe generated compositions are multifunctional, control gas channelingin naturally fractured carbonate reservoirs under ultra-high salinityenvironments, high temperature and a high concentration of divalentions; control scales problems of mineral salt that occur when theinjection and formation water are combined that are incompatible;changing the rock wettability favorably in enhanced crude-oil recoveryprocesses and control uniform corrosion problems in the production rig.

BRIEF DESCRIPTION OF THE DRAWINGS OF THE INVENTION

In order to have a better understanding about the multifunctionalfoaming composition with wettability modifying properties, corrosioninhibitory and inhibitory/dispersants of mineral scale for hightemperature and ultra-high salinity of the present invention, thendescribed briefly the contained on the accompanying drawings:

FIG. 1 shows a test system used in foam generation which consists of thefollowing parts: gas cylinder (TG-1), foam generator tube (EPM-1), lancecoupled to diffuser of 0.5μ (DF-1), flowmeter with a capacity of 0 to150 cm³/min (R-1), thermal bath with recirculation (BTR-1), arrangementof valves for controlling the gas flow (VR-1, VP-1, VP-2, VR-2, VP-3,VP-4), temperature and pressure indicators (T-1, P-1 and P2).

FIG. 2 illustrates the behavior of the foam stability at 1 kg/cm² and70° C. versus time, prepared with brine 1 described in Example 12 to 0.2Wt % of: a) cocoamido propyl hydroxysultaine, b) Mixture of the3-hidroxidodecan-1-sodium sulfonate and dodec-2-en-1-sulfonate ofsodium, c) chloride of dodecyl trimethyl ammonium, d) cocoamido propylbetaine, e) dodecyl hidroxisutaine, f) dodecyl betaine, g) Chloride ofhexadecyl trimethyl ammonium and f) foaming Composition 1.

FIG. 3 shows the behavior of the stabilities of the foams to 1 kg/cm²and 70° C. versus time, prepared with brine 1 described in Example 12 atthe 0.2 Wt % of: a) cocoamido propyl hydroxysultaine, b) mixture of3-hidroxidodecan-1-sodium sulfonate and dodec-2-en-1-sulfonate ofsodium, c) chloride of dodecyl trimethyl ammonium, d) foamingcomposition described in the Mexican patent MX 297297, e) foamingcomposition described in patent Application Mx/a/2012/014187, f) foamingcomposition 1, g) foaming composition 2 and h) foaming composition 3.

FIG. 4 indicates the behavior of the foam stability at 1 kg/cm² and 70°C. versus time, prepared with brine 1 described in Example 12 at the 0.2Wt %, with the foaming compositions 1 to 6 of the present invention.

FIG. 5 shows the behavior of the foam stability at 1 kg/cm² and 70° C.versus time, prepared with brine 1 described in Example 12 at the 0.2 Wt%, with the foaming compositions 7 to 10 of the present invention.

FIG. 6 exhibits the behavior of the stabilities of the foams to 1 kg/cm²and 70° C. versus time, prepared with the briens 2, 3 and 4 described inthe example 14 and the foaming composition 1.

FIG. 7 shows the behavior of the stabilities of the foams to 1 Kg/cm²and 70° C. versus time, prepared with the briens 2, 3 and 4 described inexample 14 and the foaming composition 2.

FIG. 8 shows the behavior of the stabilities of the foams to 1 kg/cm²and 70° C. versus time, prepared with the foaming composition 1 andbrine 4 that as described in Example 14 and using nitrogen as gas,carbon dioxide and methane and the foaming composition 1.

FIG. 9 illustrates the behavior of the stabilities of the foams to 1kg/cm² and 70° C. versus time, prepared with the foaming composition 2and the brine 4 as is described in Example 14 and using nitrogen as gas,carbon dioxide and methane.

FIG. 10 shows the evaluation equipment of the foam stability under highpressure and high temperature conditions, where: 1) temperaturecontroller, 2) BPR (back pressure regulator), 3) peephole, 4) filter. 5)cylinders of transfer 6) injection pumps, and 7) valves.

FIG. 11 shows the image sequence of the foam stability for the foamingcomposition 2, using the brine 3 whose composition are described inExample 14 at high pressure conditions and high temperature, where: 1)At the beginning of the test, 2) 1 h., 3) 18 hrs., 4) 24 hrs., 5) 36hrs., 6) 72 hrs., 7) 77 hrs., 8) 98 hrs., 9) 120 hrs., 10) 125 hrs., 11)135 hrs., 12) 142 hrs., 13) 148 hrs., 14) 167 hrs., 15) 181 hrs., 16)185 hrs., 17) 190 hrs., 18) 192 hrs., 19) 195 hrs. and 20) 240 hrs.

FIG. 12 exhibits the behavior graph of the stability of the foam fromthe foaming composition of 2 to 3500 psi (246 Kg/cm²) and 150° C. versustime, prepared with brine 3 described in Example 14.

FIG. 13 shows the graph of shear rate versus the shear stress for thefoaming composition of 2 to 3500 psi (246 Kg/cm²) and 150° C.

FIG. 14 displays the images of rock core with longitudinal court(fracture), where: a) top view, b) side view, c) longitudinal view.

FIG. 15 illustrates the device to determine the blocking factor.

FIG. 16 shows the methodology used to characterize the matrix-fracturesystem where is used the experimental equipment of the FIG. 15.

FIG. 17 shows the behavior of the pressure drop in the fracture todifferent flows of the formation water (brine 2) and the confiningpressures 1000, 1500 and 2500 psi (70, 105 and 176 Kg/cm²).

FIG. 18 exhibits the behavior of the pressure drop in the fracture todifferent flows of the foam produced from the foaming composition 2 andthe confining pressures of 1000, 1500 and 2500 psi (70, 105 and 176Kg/cm²).

FIG. 19 shows images of the foams to different flows, a) 5 mL/min b) 10mL/min.

FIG. 20 refers to the behavior of the pressure drop to differentnitrogen gas flow displacing formation water (brine 2) and foam formedwith the foaming composition 2 to a confining pressure of 2500 psi (176Kg/cm²).

FIGS. 21, 22 and 23 show the results of the displacing of oil using themultifunctional foaming Composition 2 at different concentrations. Startof the first drop displacement to different concentrations of themultifunctional foaming composition 2.

FIG. 21 illustrates the start of the first drop displacement todifferent concentrations of the multifunctional foaming composition.

FIG. 22 are refers to the just moment before of the displacement of theoil drop at different concentrations of the multifunctional foamingcomposition 2.

FIG. 23 shows the sequence of pictures of the drops displacement of oilat different concentrations of the multifunctional foaming composition2.

FIG. 24 shows the Amott cell system wherein: a) capillar where the oilproduction are observed, b) the glass body of the cell, c) rock core,and d) recirculating to maintain the temperature.

FIG. 25 displays: a) the system of Amott cells, and b) the recoveringoil in Amott cells at 90° C., using foaming compositions.

FIG. 26 shows the graph of the behavior of the recovery factor for thebrine, the foaming composition of the Mexican patent applicationMX/a/2012/014187, foaming compositions 1 to 5, 7 and 9 of the presentinvention.

FIG. 27 illustrates the graph of the behavior of the recovery factor forthe brine 5, the foaming composition of the patent applicationMX/a/2012/014187, and the foaming compositions 2 and 9 of the presentinvention.

FIG. 28 shows the graph of the behavior of the recovery factor for thebrine 6, the foaming composition of the patent applicationMX/a/2012/014187, and the foaming compositions 2 and 9 of the presentinvention.

FIG. 29 shows: a) the clean limestone core, b) the limestone core afterthe test and the recovered oil.

FIG. 30 shows the graph of the behavior of the recovery factor for thebrine 4, the foaming composition of the patent applicationMX/a/2012/014187, and the foaming compositions 2 and 9 of the presentinvention.

FIG. 31 shows the glass reactor used for imbibition process at hightemperatures, where: a) glass reactor, b) recirculating for heating, c)gas cylinder for generates the system pressure.

FIG. 32 illustrates: a) recirculator for heating, b) manometer c) safetyvalve, d) gas inlet, e) glass container, f) reactor support, g)limestone core in the imbibition test to high temperature anddisplacement of oil at 150° C.

FIG. 33 displays the image of the contact angle change of hightemperature and high pressure.

FIG. 34 shows the stacking of cores used in displacement test.

FIG. 35 presents the picture, where: a) high pressure cell andtemperature and b) stacking of cores.

FIG. 36 shows a graph which showing the oil productions by pressuredecrease.

FIG. 37 shows a graph that showing the production of oil by the foamformed injection with the foaming composition 2.

FIG. 38 shows the appearance of the metal coupons used in the dynamicwheel test, wherein: a) coupon exposed to the mixture of brine and b)coupon exposed to the foaming Composition 2.

FIG. 39 shows the appearance of the vials with brine mixture that inducethe crystals formation of calcium sulfate and that containing: a)crystals formed by mixing of brines, b) mixture of brine without crystalformation with the composition of foaming 1 c) brine mixture withoutcrystals formation with the foaming composition 2 and d) brine mixturewithout crystals formation with the foaming composition 3.

FIG. 40 illustrates the high pressure and high temperature peepholesshowing: a) Mixture of brine without chemical and at the start of thetest, b) Crystals in the brine mixture without chemical at 3 hours afterthe test started, c) mixture of brines without chemical and at the startof the test, and d) brines mixture without crystals formation with thefoaming composition 2 at 72 hours after the test started.

FIG. 41 displays the scanning electron microscopy images that showing:a) calcium sulfate crystals, b) distorted and fragmented crystals ofcalcium sulfate due to the foaming composition 2.

FIG. 42 shows the scanning electron microscopy images that showing: a)calcium carbonate crystals, and b) distorted and fragmented crystals ofcalcium carbonate due to the foaming composition 2.

FIG. 43 shows the structure of a product resulting from thesupramolecular interaction of alkyl amido propyl hydroxysultaines oralkyl hydroxysultaines with alkyl hydroxysulfonates of sodium andalkenyl sulphonates of sodium, as described in Mexican patentapplication MX/a/2012/014187.

DETAILED DESCRIPTION OF THE INVENTION

The present invention are relates to the obtaining and use ofmultifunctional foaming compositions that control gas channeling innaturally fractured carbonate reservoirs under high temperature andultra-high salinity conditions, changing the rock wettability favorablyin enhanced recovery processes, inhibit the uniform and localizedcorrosion of ferrous metals and inhibit and disperse scale of calciumcarbonate and calcium sulfate, barium and strontium, these last the maincauses of formation damage.

The multifunctional properties are generated by compositions thatcontains supramolecular complexes resulting from the interactions ofalkyl amido propyl hydroxysultaines and/or alkyl amido propyl betainesand/or alkyl hydroxysultaines and/or alkyl betaines and anionicsurfactants of the type alkyl hydroxy sulfonates of sodium and alkenylsulfonates sodium, with cationic surfactants tetra-alkyl ammoniumhalydes and copolymers derivatives of itaconic acid/sodium vinylsulfonate and/or terpolymers derived from itaconic acid/sodium vinylsulphonate/aconitic acid.

The multifunctional compositions of the present invention arecharacterized by having high stability in high-temperature, highpressure and possess tolerance to high concentrations of divalent ionslike calcium, magnesium, strontium and barium. For the development ofthe present invention, a process which consists of the followingsteps: 1) obtaining of multifunctional compositions, and 2) experimentalevaluation of foam properties, wettability modifying, uniform andlocalized corrosion inhibitory and inhibition and dispersion of mineralscale as calcium carbonate, calcium sulfate, barium and strontium.

1) Obtaining Multifunctional Foaming Compositions.

The multifunctional foaming compositions of this invention are obtainedby combining supramolecular complexes resulting from interactions ofalkyl amido propyl hydroxysultaines and/or alkyl amido propyl betainesand/or alkyl hydroxysultaines and/or alkyl betaines and anionicsurfactants of the type alkyl hydroxy sulphonates os sodium and alkenylsulphonates of sodium, with cationic surfactants as tetra-alkyl ammoniumhalides and copolymers derived from itaconic acid/vinyl sodium os sodiumand/or terpolymers derived from itaconic acid/sodium vinylsulphonate/aconitic acid, in different proportions. The followingexamples will be served to illustrate the preparation of themultifunctional foaming compositions, object of the present invention.

Example 1

Obtaining of the multifunctional foaming composition 1 from thecombination of supramolecular complexes derived from the interactions ofcoco-amido-propyl hydroxysultaine with 3-hidroxidodecan-1-sulfonate anddodec-2-en-1-sodium sulfonate with chloride of dodecyl trimethylammonium: Composition A, following the procedure described in Mexicanpatent application MX/a/2012/014187 (Composición espumante conpropiedades modificadoras de la mojabilidad e inhibitorias de lacorrosion para alta temperatura y ultra alta salinidad), are mixed at atemperature of 50° C. and atmospheric pressure in a two-necked roundflask of 1000 ml, equipped with a magnetic stirrer and a thermometer,160.6 g of distilled water with 250.0 g of an aqueous solution thatcontain 43.5 Wt % (0.278 mol) of coco-amido-propyl hydroxysultaine and81.0 g of an aqueous solution containing 47.8 Wt % of a mixture of3-hidroxidodecan-1-sodium sulfonate and dodec-2-en-1-sulfonate ofsodium, and which is characterized by possess 47.4 Wt % (0.0636 mol) of3-hidroxidodecan-1-sodium sulfonate and 52.6 Wt % (0.0753 mol) ofdodec-2-en-1-sulfonate of sodium. The mixture is stirred for 3 hours togive rise to 490.7 g of the composition A, as a viscous amber-yellowliquid.

Composition B: Are mixed at room temperature and atmospheric pressure ina two-necked round flask of 250 ml, equipped with a magnetic stirrer anda thermometer, 39.86 g of an aqueous solution containing 37 Wt % (0.056mol) of dodecyl trimethyl ammonium chloride with 50.39 g of an aqueoussolution containing 43.5 Wt % (0.056 mol) of coco-amido-propylhydroxysultaine and 32.01 g of distilled water.

The reaction mixtures are stirred for 30 minutes to give rise to 122.26g of the B composition, as a slightly-viscous amber-yellow liquid.Finally, in a two-necked round flask of 1000 ml, equipped with amagnetic stirrer and a thermometer, are mixed 490.7 g of the compositionA with 122.26 g of the composition B, at a temperature of 50° C. andatmospheric pressure with stirring for 3 hours to give rise to 614 g ofthe multifunctional foaming composition 1 as a viscous amber-yellowliquid containing 30 Wt % of active compound.

Example 2

Obtaining the multifunctional foaming composition 2, from thecombination of supramolecular complexes derived from the interactions ofcoco-amido-propyl hydroxysultaine with 3-hidroxidodecan-1-sodiumsulfonate and dodec-2-en-1-sodium sulfonate with dodecyl trimethylammonium chloride and a copolymer derived from itaconic acid and vinylsulfonate of sodium: In a two-necked round flask of 1000 ml, equippedwith a magnetic stirrer and a thermometer, are mixed at a temperature of50° C. and atmospheric pressure with continuous stirring of 614 g of themultifunctional foaming composition described in Example 1 with 34.2 gof an aqueous solution containing 50 Wt % of a copolymer derived fromitaconic acid and vinyl sodium sulfonate and 22.8 g of distilled water.At the end of 1 hour of stirring, it was obtained 671 g of themultifunctional foaming composition 2 as a viscous amber-yellow liquidcontaining 30 Wt % of active product.

Example 3

Obtaining the multifunctional foaming composition 3 from the combinationof supramolecular complexes resulting from interactions of lauryl andmyristyl amido-propyl betaines with 3-hidroxidodecan-1-sulfonate anddodec-2-en-1-sulfonate with hexadecyl trimethyl ammonium chloride and acopolymer derived from itaconic acid and sodium vinyl sulfonate:

Composition C: In a two-necked round flask of 1000 ml, equipped with amagnetic stirrer and a thermometer, were mixed at a temperature of 50°C. and atmospheric pressure with constant agitation, 146.6 g ofdistilled water, 361.2 g of an aqueous solution containing 32.70 Wt % ofa mixture of lauryl and myristyl amido-propyl betaines and 192.2 g of anaqueous solution containing 47.8 Wt % of a mixture of3-hidroxidodecan-1-sodium sulfonate and dodec-2-en-1-sulfonate ofsodium, and which are characterized by possess 47.4 Wt % (0.0636 mol) of3-hidroxidodecan-1-sodium sulfonate and 52.6 Wt % (0.0753 mol) ofdodec-2-en-1-sulfonate sodium. The mixture is vigorously stirred for 3hours to give rise to 700 g of C composition as a viscous amber-yellowliquid.

Composition D: Are mixed at room temperature and atmospheric pressure ina two-necked round flask of 250 ml, equipped with a magnetic stirrer anda thermometer, 81.5 g of an aqueous solution containing 30.4 Wt % (0.056mol) of chloride of hexadecyl trimethyl ammonium with 84.8 g of anaqueous solution containing 32.7 Wt % of a mixture of lauryl andmyristyl amido-propyl betaines and 8.64 g of distilled water. Thereaction mixture is stirred for 30 minutes to give rise to 175 g of theD composition as a slightly-viscous amber-yellow liquid.

Finally, in a two-necked round flask of 1000 ml, equipped with amagnetic stirrer and a thermometer, are mixed at a temperature of 50° C.and an atmospheric pressure, 15.8 g of distilled water, 700 g of Ccomposition, 175 g of D composition and 23.9 g of an aqueous solutioncontaining 50 Wt % of a copolymer derived from sodium vinyl sulfonateand itaconic acid, with continuous stirring for 4 hours to give rise to914.7 g of the multifunctional foaming composition 3 as a viscousamber-yellow liquid containing 30 Wt % of active product.

Example 4

Obtaining of the multifunctional foaming composition 4, from thecombination of supramolecular complexes resulting from the interactionsof lauryl betaine, 3-hidroxidodecan-1-sodium sulfonate anddodec-2-en-1-sodium sulfonate with chloride of dodecyl trimethyl ammoniaat a: two-necked round flask of 1000 ml, equipped with a magneticstirrer and a thermometer, are mixed at a temperature of 48° C. andatmospheric pressure with continuous stirring, 67 g of distilled water,350 g of an aqueous solution containing 30 Wt % of lauryl betaine and112.9 g of an aqueous solution containing 47.8 Wt % of a mixture of3-hidroxidodecan-1-sodium sulfonate and dodec-2-en-1-sulfonate ofsodium, and which is characterized by possess 47.4 Wt % (0.0636 mol) of3-hidroxidodecan-1-sodium sulfonate and 52.6 Wt % (0.0753 mol) ofdodec-2-en-1-sulfonate of sodium.

The mixture is vigorously stirred for 3 hours to give rise to 529.9 g ofa viscous amber-yellow liquid containing 30 Wt % of the E composition.On the other hand, gets ready a composition F, consisting of 53.3 g ofan aqueous solution containing 37 Wt % of dodecyl trimethyl ammoniumchloride with 67.6 g of an aqueous solution containing 30 Wt % of laurylbetaine and 12.4 g is of distilled water. The F composition wascontinuously stirred for 30 minutes to give rise to 133.4 g of aslightly-viscous amber-yellow liquid. Finally, in a two-necked roundflask of 1000 ml, equipped with a magnetic stirrer and a thermometer,they are mixed at a temperature of 48° C., atmospheric pressure andcontinuous stirring, 529.9 g of E composition and 133.4 g of the Fcomposition for 3 hours, to give rise to 663.3 g of the multifunctionalfoaming composition 4 as a viscous amber-yellow liquid containing 30 Wt% of active product.

Example 5

Obtaining of the multifunctional foaming composition 5, from thecombination of supramolecular complexes resulting from interactions oflauryl betaine with 3-hidroxidodecan-1-sodium sulfonate anddodec-2-en-1-sodium sulfonate with dodecyl trimethyl ammonium chlorideand a copolymer derived from itaconic acid and sodium vinyl sulfonate:in a two-necked round flask of 1000 mL, equipped with a magnetic stirrerand a thermometer, are mixed at a temperature of 50° C. and anatmospheric pressure with constant agitation, 663.3 g of the product 4described in Example 4, 36.9 g of an aqueous solution containing 50 Wt %of a copolymer derived from itaconic acid and sodium vinyl sulfonate and24.6 g of distilled water to give rise to 724.9 g of the foamingcomposition multifunctional 5 as a viscous amber-yellow liquidcontaining 30 Wt % of active product.

Example 5

Obtaining of the multifunctional foaming composition 6, from thecombination of supramolecular complexes resulting from interactions ofdodecyl hydroxy sultaine with 3-hidroxidodecan-1-sodium sulfonate anddodec-2-en-1-sodium sulfonate with dodecyl trimethyl ammonium chloride:In a two-necked round flask of 1000 ml, equipped with a magnetic stirrerand a thermometer, were mixed at a temperature of 48° C., atmosphericpressure and continuous stirring, 224.1 g of distilled water, 250 g ofan aqueous solution containing 49 Wt % (0.380 mol) ofdodecyl-hydroxysultaine with 110.9 g of an aqueous solution containing47.8 Wt % of a mixture of 3-hidroxidodecan-1-sodium sulfonate anddodec-2-en-1-sulfonate of sodium, and which is characterized by possess47.4 Wt % (0.087 mol) of 3-hidroxidodecan-1-sodium sulfonate and 52.6 Wt% (0.100 mol) of dodec-2-en-1-sulfonate of sodium. The mixture isvigorously stirred for 3 hours to give rise to 584.8 g of a viscousamber-yellow liquid containing 30 Wt % of the G composition. On theother hand, gets ready an H composition composed of 53.4 g of an aqueoussolution containing 37 Wt % (0.075 mol) of dodecyl trimethyl ammoniumchloride with 49.3 g of an aqueous solution containing 49 Wt % (0.075mol) of dodecyl hydroxysultaine and 43.6 g of distilled water. The Hcomposition is stirred for 30 minutes to give rise to 146.2 g of aslightly viscous liquid of amber color. Finally, in a two-necked roundflask of 1000 ml, equipped with a magnetic stirrer and a thermometer,584.8 g of the G composition are mixed with 146.2 g of the Hcomposition, at a temperature of 50° C. and atmospheric pressure withstirring for 3 hours to give rise to 731 g of the foaming compositionmultifunctional 6 as a viscous amber-yellow liquid containing 30 Wt % ofactive product.

Example 7

Obtaining of the multifunctional foaming composition 7, from thecombination of supramolecular complexes resulting from the interactionsof lauryl-hydroxy sultaine with 3-hidroxidodecan-1-sodium sulfonate anddodec-2-en-1-sodium sulfonate with dodecyl trimethyl ammonium chlorideand a copolymer derived from itaconic acid and sodium vinyl sulfonate:In a two-necked round flask of 1000 ml, equipped with a magnetic stirrerand a thermometer, are mixed at a temperature of 50° C. and atmosphericpressure with continuous stirring, 731 g of product 6 described inExample 6, 40.7 g of an aqueous solution containing 50 Wt % of acopolymer derived from itaconic acid and sodium vinyl sulfonate and 27.3g of distilled water to give rise to 799 g of the foaming compositionmultifunctional 7 as a viscous amber-yellow liquid containing 30 Wt % ofactive product.

Example 8

Obtaining the multifunctional foaming composition 8, from thecombination of supramolecular complexes derivatives from theinteractions of coco-amido-propyl hydroxysultaine with3-hidroxidodecan-1-sulfonate and dodec-2-en-1-sodium sulfonate withdodecyl trimethyl ammonium chloride and a zwitterionic germinal liquidlinear type bis beta-N-alkenyl-N-polyether beta amino acid derived ofthe oleyl amine: In a two-necked round flask of 1000 ml, equipped with amagnetic stirrer and a thermometer, are mixed at a temperature of 50° C.and atmospheric pressure with continuous stirring, 614 g of the product1 described in Example 1, 27.3 g of an aqueous solution containing 30 Wt% of a zwitterionic geminal liquid linear type bis-N-alkenyl-N-polyetherbeta amino acid derived of the oleylamine to give rise to 641.3 g of thefoaming composition multifunctional 8 as a viscous amber-yellow liquidcontaining 30 Wt % of active product.

Example 9

Obtaining of the multifunctional foaming composition 9, from thecombination of supramolecular complexes derivatives from theinteractions of coco-amido-propyl hydroxysultaine with3-hidroxidodecan-1-sodium sulfonate and dodec-2-en-1-sodium sulfonatewith dodecyl trimethyl ammonium chloride, a copolymer derived from theitaconic acid and vinyl sodium sulfonate and a zwitterionic geminalliquid linear type bis-N-alkenyl-N-polyether beta amino acid derivativeof the oleylamine: in a two-necked round flask of 1000 ml, equipped witha magnetic stirrer and a thermometer, are mixed at a temperature of 50°C. and atmospheric pressure with continuous stirring, 671 g of thecomposition described in Example 2, 29.4 g of an aqueous solutioncontaining 30 Wt % of a zwitterionic geminal liquid linear typebis-N-alkenyl-N-polyether beta amino acid derivative of oleylamine togive rise to 770.4 g of the foaming composition multifunctional 9 as aviscous amber-yellow liquid containing 30 Wt % of active product.

Example 10

Obtaining of the multifunctional foaming composition 10, from thecombination of supramolecular complexes derivatives from theinteractions of coco-amido-propyl hydroxysultaine with3-hidroxidodecan-1-sodium sulfonate and dodec-2-en-1-sodium sulfonatewith dodecyl trimethyl ammonium chloride and a terpolymer derived fromitaconic acid/sodium vinyl sulfonate/aconitic acid: In a two-neckedround flask of 1000 ml, equipped with a magnetic stirrer and athermometer, are mixed at a temperature of 50° C. and atmosphericpressure with continuous stirring, 614 g of the composition described inExample 1, 57 g of an aqueous solution containing 30 Wt % of aterpolymer derivative of itaconic acid/sodium vinyl sulfonate/aconiticacid to give rise to 671 g of the multifunctional foaming composition 10as a viscous amber-yellow liquid containing 30 Wt % of active product.

2) Experimental Evaluation of Foam, Wettability Modifying, Adsorption,Inhibitory Uniform and Localized Corrosion Properties andInhibition/Dispersion of Mineral Scale of Calcium Carbonate, CalciumSulfate, Barium and Strontium:

I) Evaluation of the Foaming Properties:

The evaluation of the foam ability of the foaming compositionsmultifunctional generated from the combination of supramolecularcomplexes derivatives from the interactions of alkyl amido propylhydroxysultaines and/or alkyl amido propyl betaines and/or alkylhydroxysultaines and/or alkyl betaines with anionic surfactants of thetype alkyl hydroxy sulphonates of sodium and alkenyl sulphonates ofsodium, with cationic surfactants as tetra-alkyl ammonium halides andcopolymers derived from itaconic acid/vinyl sulfonate sodium and/orterpolymers derived from itaconic acid/vinyl sulfonate sodium/aconiticacid, object of the present invention was performed through threedifferent tests: a) Measurement of the foam stability to atmosphericpressure conditions, b) Measurement of the foam stability in conditionsof high pressure and high temperature, c) Determination of rheologicalbehavior in a capillary rheometer at reservoir conditions, and d)Determination blocking factor.

a) Measurement of the Foam Stability at Atmospheric Pressure Conditions.

The foam generation system at atmospheric pressure, which was used, is amodification of the system described in the Mexican patent MX 297297 andis designed to evaluate the stability of foams generated by surfactantsat temperatures of up to 70° C. and it is shown in FIG. 1. The foamingsystem consists of three subsystems, the first are composed by the foamgenerator body formed by two concentric glass tubes. The outer tube is1.35 m of high with a diameter of 0.0762 m and the inner tube has aheight of 1.15 m, with a diameter of 0.0508 m. In the inner tube isloaded the solution to evaluate (brine plus chemical) and is carried outthe generation and confinement of the foam. Whereas the outer tube hasthe function of contain the heating liquid, whereby the test temperatureis controlled. The second subsystem is the one that controls the gasflow and consists of a storage tank, whereby, are regulate the dischargepressure of the gas and a second tank of stabilization of smallerdimensions whose function is precisely to contribute to the regulationof gas flow and prevent the condensate skidding. In the gas line it ishas an array of three valves to control the direction and magnitude ofthe gas flow, the first is a venting valve connected to the stabilizingtank, then is counted has a bypass valve, that allows the gas supplyinto a calibrated flowmeter (maximum flow of 3 SFC/h) and finally athree-way valve used to control the flow of gas into the body of foamgenerator as well as opening system to the atmosphere. At the end ofthis subsystem, It has a stretch of stainless steel tubing or lance inwhich lower end it is attached a disperser- or diffuser-sintered (whichmay be of glass or steel), through which the gas is injected the liquidphase in order to evenly distribute the gas flow and achieve amonodisperse foam texture. Finally the third subsystem is thetemperature control which is made in the annular space through anoil-heating flow, controlled by a heat bath of digital recirculation. Tocarry out the measurement of foam stability and foaming capability, aprocess consisting of 18 stages was developed and are describedbelow: 1) Prepare the study solution to the required concentration forthe analysis; 2) Check the cleanliness of the inner glass tube; 3) Turnon the thermal bath and fix a temperature of 70° C. (the process takesabout 1 hour); 4) Open the gas valve of the tank; 5) vent valves bothfrom the gas tank as well as the foam generator; 6) Ensure that thepressure is at 50 psi (3.5 Kg/cm²); 7) Inject 60 ml of the solution tobe tested via syringe and a hose; 8) Introduce and center the steelspear and leave for 10 minutes to homogenize the temperature in thespear; 9) Connect the gas line to the spears; 10) Place a heating bandat the top of foam generator in to the order of avoid the vaporscondensation; 11) Record the initial height of the liquid; 12) Open thegas shutoff valve; 13) Open the rotameter and control the flow toreaching 50 psi and keep it; 14) Start the timer as soon as the firstgas bubble appears in the fluid; 15) After 45 seconds to shut off thegas valve, open the gas venting valve and measuring the foam- andliquid-height (maximum height) and as well as reset the timer; 16) takemeasurements of the heights of the foam and the liquid every minute for10 minutes to determine the speed of drain and foam quality; 17) Recordthe heights of the foam and liquid every 10 minutes until the foamheight reaches 30% of the maximum height and 18) Determine thepercentage of the foam stability each time and on this basis build adiagram foam stability over time. The foam stability is defined as thechange in initial foam height versus time and is determined according toEquations 1 and 2.H _(t) −H _(L) =H _(e)  Equation 1where:

-   -   H_(e)=Foam height.    -   H_(L)=solution height.    -   H_(t)=total height of experiment

The experiment was terminated when 30% of the foam stability is reached.

The calculation for the foam stability is as follows:

$\begin{matrix}{{\frac{H_{e}}{H_{eMAX}} \times 100} = E} & {{Equation}\mspace{14mu} 2}\end{matrix}$were:

-   -   H_(e)=Foam height.    -   H_(eMAX)=maximum height of the foam.    -   E=foam stability.        where H_(eMAX is) the H_(e) calculated at 45 seconds of the        experiment.

In order to demonstrate that the foaming compositions of the presentinvention possess great advantages over components used as raw materialsfor formation, it was determined the foam stability generated by: cocoamido propyl hydroxysultaine, mixture of 3-hidroxidodecan-1 sodiumsulfonate and dodec-2-en-1-sodium sulfonate, dodecyl trimethyl ammoniumchloride, cocoamido propyl betaine, dodecyl hidroxisultaine, dodecylbetaine and hexadecyl trimethyl ammonium chloride and the results werecompared with the multifunctional foaming composition 1 of the presentinvention.

Example 11

Determination the foam stability generated by: a) cocoamido propylhydroxysultaine, b) mixture of 3-hidroxidodecan-1-sodium sulfonate anddodec-2-en-1-sodium sulfonate, c) dodecyl trimethyl ammonium chloride,d) cocoamido propyl betaine, e) dodecyl hidroxisultaine, f) dodecylbetaine, g) hexadecyl trimethyl ammonium chloride, h) multifunctionalfoaming composition 1. The stability of the generated foam by thecommercial surfactant and the foaming composition 1 was evaluatedthrough the foaming test at atmospheric pressure, at a temperature of70° C. using brine 1 containing 32804 ppm of total dissolved solids, ofthe which they corresponded to 1736 ppm corresponding to divalent ions(calcium and magnesium), 6420 ppm as a total hardness of CaCO₃ and aconcentration of the commercials surfactants and the foaming composition1 in 0.2 Wt %. To Form all the foams nitrogen gas (N₂) was used. InTable 1 are show the composition of the brine 1, used to dilute thecommercial surfactants and the multifunctional foaming composition 1.The time set for obtain each parameter (foam- and liquid-height) was 45s and the minimum percentage of foam stability recorded was 30%. In theFIG. 2 are observed the behavior of the foams stability to 1 kg/cm² and70° C. versus time, prepared with brine 1 to 0.2 Wt % of the commercialsurfactant and the multifunctional foaming composition 1. In this graphare shows that the minimum stability at 30% is achieved for commercialsurfactant in the range of 10 to 50 min, while for the foamingcomposition 1 are reached to about 440 min. The above evidence thetechnical advantage of the multifunctional foaming composition 1 withrespect to commercial surfactants.

TABLE 1 Compositions of Brine 1. Brine 1 mg/L Cations Sodium 11742.1Calcium 448 Magnesium 1288.4 Anions Chlorides 19900 Sulfates 3650Carbonates 13.2 Bicarbonates 84.2 Total hardness as CaCO₃ 6420 Salinityas NaCl 32803.9

In order to demonstrate that the foaming compositions of the presentinvention, possess considerable advantages on the components used as rawmaterials for its formation as well as of agents reported in otherpatents, it carried out his evaluation and it was compared the resultswith the multifunctional foaming compositions of the present invention.

Example 12

Determination of the stability of foams generated with brine 1 andnitrogen for: a) cocoamido propyl hydroxysultaine, b) mixture of3-hidroxidodecan-1-sodium sulfonate and dodec-2-en-1-sodium sulfonate,c) dodecyl trimethyl ammonium chloride, d) foaming composition describedin Mexican patent MX 297297, e) foaming composition described in thepatent application MX/a/2012/014187, f) multifunctional foamingcomposition 1, g) multifunctional foaming composition 2 and h)multifunctional foaming composition 3. The obtained results of foamsstability in the foaming test at atmospheric pressure and aconcentration of 0.2 Wt % showing in FIG. 3. The analysis of resultsshows that the minimum stability of 30% for the multifunctional foamingcomposition 1, 2 and 3 is achieved in times of 440, 500 and 400 minutesrespectively. The above, indicates that the stability of the foamsgenerated by the compositions of the present invention exceed by morethan 10 times to those generated from commercial surfactants, in morethan 2 times to the foaming composition of the MX Patent 297297 and inmore than 80 minutes to the foaming composition of the foamingapplication MX/a/2012/014187.

Example 13

Determination of the foam stability generated with the brine 1 and themultifunctional foaming compositions 1 to 10: The obtained results aboutof foam stability of the foaming test at atmospheric pressure and aconcentration of 0.2 Wt % of the foaming compositions 1 to 6 showing inFIGS. 4 and 5, showing the results for the compositions 7 to 10.

The analysis of the results indicates that the minimum stability of 30%for the multifunctional foaming compositions 1 to 10 is achieved attimes ranging from 390 to 510 minutes.

Example 14

It was carried out the evaluation of the foamability of multifunctionalfoaming compositions 1 and 2 of the present invention in three brine(formation water) of different composition of high salinity with a highcontent of divalent ions (calcium, magnesium, barium and strontium) andsalinity as NaCl.

The characteristics of the formation water used to generate the foamshowing in Table 2.

TABLE 2 Compositions of the brine 2, 3 and 4. Brine 2 Brine 3 Brine 4 pH7.33 6.38 4.96 mg/L mg/L mg/L Cations Sodium 44223.39 59809.46 52559Calcium 12720 31880 56800 Magnesium 826.54 1944.8 2917 Estroncium 7101450 ND Barium 1.84 25.33 ND Anions Chlorides 92800 154000 190000Sulfates 225 300 5 Bicarbonates 256.2 148.84 82.96 Total hardness asCaCO₃ 35200 87700 154000 Salinity as NaCl 152974.86 253859.14 313203

The obtained results of the foam stability in the foaming test atatmospheric pressure and a concentration of 0.2 Wt % of themultifunctional foaming compositions 1 and 2 showing in FIGS. 6 and 7,respectively.

The analysis of the results indicates that the minimum stabilities of30% for the multifunctional foaming compositions 1 and 2 in the highsalinity brines 2, 3 and 4 are achieved in longer times to 600 minutes.

Example 15

Was carried out evaluation of the foamability for the multifunctionalfoaming compositions 1 and 2 of the present invention at atmosphericpressure, at a temperature of 70° C., and using the brine 4 thatcontaining a salinity of 313,203 ppm as NaCl, from which 154,000 ppmcorresponded to divalent ions (calcium and magnesium), a concentrationof the foaming compositions of 0.2 Wt % as nitrogen gas (N₂), methane(CH₄) and carbon dioxide (CO₂).

The obtained results of the foam stability in foaming test atatmospheric pressure and a concentration of 0.2 Wt % of multifunctionalfoaming compositions 1 and 2 with methane-, carbon dioxide- andnitrogen-gas showing in FIGS. 8 and 9, respectively at 1 kg/cm² and 70°C.

The analysis of the results indicates that the stability achieved ismaintained for all the cases greater than 60% over 700 minutes.

b) Foaming Test at High Pressure:

The system of generating foam to high pressure is made from a PVT cell(pressure, temperature, volume) adapted as shown in FIG. 10 (PVT celladapted and used for foam stability test at high-pressure and-temperature). The PVT cell consists of a BPR valve, whose purpose is tomaintain the working pressure in the system and permit injection offluids. Inside the cell and at the bottom was adapted a disperser,through which the gas is injected, into this same part an inlet for theinjection of brine with the formulated foaming was adapted. The foam isgenerated within a sapphire tube; into this tube exists a piston thatmoves to allow the fluid entry, the space between the piston and the BPRvalve is filled with a mineral oil with which it is possible to controlthe height piston. To carry out the measurement of foam stability andability of foaming, a process consisting of 11 stages was developed anddescribed below: 1) Prepare the PVT cell (FIG. 10) with thecorresponding adjustments to the test foams; 2) Open the valves of thecell and connect the vacuum pump for 30 minutes; 3) is injecting gasinto the cell, to get inside the cell the corresponding pressure to thetest pressure and the height of the piston to −0.327; 4) Inject thevolume of foaming agent (50 cm³); 4) Record the height of the foamingagent with respect to its reference and the height of the piston withthe charged foaming; 5) Place the gas cylinder at a pressure of 150kg/cm²; 6) Note the difference in height between liquid and foam (ifany); 6) Record the starting time of the test; 7) Inject the gas intothe system through the disperser for 5 seconds counted by timer; 8)Suspend the gas injection and wait for the pressure of the gas cylinderscope 150 kg/cm² and record the volume of injected gas; 9) Record theinitial foam height and start taking the foam- and liquid-height everyten minutes until the foam completely down and the foaming liquid scopethe initial stage of the test; 10) Determine the % of the foam stabilityat each time.

The system of foam generation at high pressure and high temperature thatwas used was developed in the laboratory of hydrocarbon recovery of theMexican Petroleum Institute (Instituto Mexicano del Petróleo) and isdesigned to evaluate the stability of foams generated by surfactants attemperatures of up to 170° C. and pressures up to 6000 psi (423 Kg/cm²)and the same is shown in FIG. 10, which consists of injection pumps,transfer cylinders, back pressure regulator (BPR), temperature controlsystem, pressure monitoring system, digital camera, filter (foamgenerator) and experimental cell.

1) Test Conditions

-   -   Temperature: 150° C.    -   Pressure: 3,500 psi (246 Kg/cm²)    -   Gas: Nitrogen    -   Brine 4    -   Test time: 11 days    -   Liquid Spending: 0.6 ml/min    -   Gas Spending: 2.4 ml/min        2) Methodology:        1) Conditioning of the system:    -   Peephole    -   BPR    -   Cylinders of transfer        2) The pressure transducer and thermocouples were calibrated.        3) The temperature is raised at which it is carry out the        experiment and the pressure is maintained by the BPR valve.        4) The liquid additive with chemical and the gas is injected to        form the foam in a ratio of 1 to 4, respectively under reservoir        conditions.        5) Once formed the foam and saturated cell the system is        isolated and allowed to monitor the pressure and temperature.        6) Photographic images are taken at different times during the        test to observe the stability of the foam.        Determination of the Foam Stability.

The methodology for determining the stability of the foam it is asfollows:

1. Is carried out a color scale to gray scale for the photographicimages.

2. It is calculated the peephole area in pixels.

3. It is calculated the lamella free area.

4. It is calculated the percentage of free area of lamella.% of free area of lamella=free area of lamella/Area ofPeephole  Equation 35. It is calculated the percentage of area of lamella.% of area of lamella=1−% free area of lamella  Equation 4

Example 16

Was carried out the evaluation of the stability of the foam formed bythe multifunctional foaming composition 2, through the foaming test athigh pressure, which conditions are 3,500 psi (246 Kg/cm²) pressure and150° C., using the brine 4 that containing 313,203 ppm of salinity asNaCl, of which corresponded to 154,000 ppm of divalent ions (calcium andmagnesium), a supramolecular complex concentration of 0.2 Wt % and asgas nitrogen (N₂). In FIG. 11 is shown the sequence of images of theformed foam by brine plus multifunctional foaming composition 2 at aconcentration of 0.2 Wt %, whereby the foam behavior is observed duringthe test. The duration of the formed foam by the multifunctional foamingcomposition 2 was around of 240 hours whose data showing in Table 3, atwhich time the system conditions were kept constant at 150° C. and 3,500psi (246 Kg/cm²) of pressure. In FIG. 12 it is shown the time behavioragainst the foam stability at reservoir conditions for multifunctionalfoaming composition 2. With the above are demonstrated the technologyadvantage of using multifunctional foaming compositions of the presentinvention under high pressure 3500 psi (246 Kg/cm²), high temperature(150° C.) and ultra-high salinity brines and high hardness conditionsand its versatility of using different gases to produce the foam.

c) Determination of Rheological Behavior in Capillary Rheometer atReservoir Conditions.

The test method consists in determine the rheological behavior of foamsgenerated from the foaming compositions object of the present invention,with ultra-high salinity water and high hardness under reservoirconditions using a capillary rheometer for high pressure and hightemperature using a experimental method developed in the laboratory ofwell productivity of the Mexican Petroleum Institute, in which thepressure drop between two points of the capillary tube as a function ofspending foam is determined.

TABLE 3 % Area of lamella Time (h) 100 0 90 5 90 10 90 15 90 25 80 30 8035 80 50 80 55 72 60 72 70 72 75 72 80 72 95 72 100 72 105 72 110 72 12072 130 72 135 72 140 63 145 63 160 63 165 55 170 55 180 45 190 45 200 45210 45 220 40 230 28 240Required Elements for Testing:

-   -   Capillary rheometer for high pressures and temperatures.    -   Nitrogen tank.    -   1 L of solution of foaming agent in characteristic brine.        Test Procedures:    -   1) Carrying the system of the capillary rheometer at the        temperature and pressure of the experiment.    -   2) Fix the total spending or the spending of foam according to        the dimensions of the capillar tube to obtain the maximum shear        rate desired, the Volumetric flow rate (VFR) of nitrogen gas and        foam solution will be defined for obtained the required quality.        This relation should conform to the following equation:

$\begin{matrix}{{Quality} = \frac{Qgas}{{Qgas} + {Qliq}}} & {{Equation}\mspace{14mu} 5}\end{matrix}$where the total spending is given by the sum of the VFR of gas andliquid.

-   -   3) For a fixed total spending, recording the values of pressure        drop corresponding in a time interval of 10 minutes.    -   4) Modify the total spending to a lower value and re-register        the values of pressure drop for the same period of time than in        previous point.    -   5) Repeat the procedure until obtain at least 7 points or 7        different VFR.    -   6) Based on the experimental data of the total volume spending        and pressure drop calculate the shear stress and the shear rate        corresponding, in order to obtain the graph of shear stress        versus shear rate, from which can be seen and determine the        rheological behavior of the foam.    -   7) Perform a mathematical adjustment according to the type of        curve observed for obtaining the rheological model equation of        the foam where the apparent viscosity can be calculated as a        function of shear rate.

Example 17

Was carried out the determination of the rheological behavior of a foamgenerated by the multifunctional foaming composition 2 at a temperatureof 150° C. and pressure of 3500 psi (246 Kg/cm²), at a concentration of0.2 Wt % in the brine 4 described in the Example 15 and using asnitrogen gas to achieve a quality of 80% and in a range of high shearrate. In Table 4 are summarized the principal conditions of theexperiment and dimensions of the capillary.

From the obtained results and to perform the mathematical adjustment ofthe rheological behavior for this foam with a correlation coefficientR²=0.9706 was found as characteristic equation of a pseudoplastic fluid:μ=779.4×γ^(0.3945-1)  Equation 6where the viscosity μ calculated directly in centipoises and γ the shearrate is given in s⁻¹.

TABLE 4 Temperature: 150° C. Pressure: 3500 psi (246 Kg/cm²) shear rateinterval: 74-650 s⁻¹ Internal diameter: 0.119 cm length: 60 cm Foamquality: 80%

Then in Table 5 and FIG. 13 are shows the results obtained.

TABLE 5 Q ΔP shear rate (cm³/h) (Pa) (1/s) 700.00 158400 649.67 600.00151800 556.86 500.00 136800 464.05 400.00 136400 371.24 300.00 127600278.43 250.00 127600 232.02 200.00 114400 185.62 150.00 101200 139.21100 85800 92.81 80 55000 74.25

From the above equation it is possible to calculate the viscosity as afunction of shear rate, the results shown in Table 6.

From the results obtained in this evaluation for the foam generated fromthe multifunctional foaming composition 2 it shows that even at highcutting speeds of 649.7 s⁻¹ under pressure and reservoir temperatureconditions may reach values of viscosity of 14.45 cP, this is 72 timesmore than water and 723 times more than the viscosity of nitrogen.

TABLE 6 Experimental Apparent shear rate (1/s) Viscosity (cP) 649.6714.45 556.86 16.16 464.05 17.47 371.24 21.78 278.43 27.16 232.02 32.59185.62 36.53 139.21 43.08 92.81 54.79 74.25 43.90

Example 18

Was carried out the determination the rheological behavior of a foamgenerated by the multifunctional foaming composition 2 at a temperatureof 150° C. and pressure of 3500 psi (246 Kg/cm²) at a concentration of0.2 Wt % in the brine 4 whose composition are described in Example 15,using as nitrogen gas to achieve a quality of 80% and in a range of lowshear rate.

In Table 7 are summarized the principal conditions of the experiment andthe dimensions of the capillary.

TABLE 7 Temperature: 150° C. Pressure: 3500 psi (246 Kg/cm²) Shear rateinterval: 9-75 s⁻¹ Internal diameter: 0.255 cm length: 610 cm Foamquality: 80%

Then in Table 8 are shows the results obtained.

TABLE 8 Q ΔP Shear rate (cm³/h) (Pa) (1/s) 80.00 52000.00 74.25 60.0046,500.00 55.69 40.00 37000.00 37.12 20.00 24,350.00 18.56 10.0022101.00 9.28 5.00 14,678.00 4.64

From the results obtained and to perform the mathematical adjustment ofthe rheological behavior for this foam with a correlation coefficientR²=0.9581 was found as characteristic equation of a pseudoplastic fluid:μ=441.5×γ^(−0.5529)  Equation 7

From the above equation it is possible to calculate the viscosity as afunction of Shear rate, the results shown in Table 9. From the resultsobtained of this evaluation for the foam generated from the foamingcomposition 2 it shows that at low share rate, close to those found atthe reservoir about 9 s⁻¹ under pressure and temperature reservoirsconditions can be achieved viscosity values of 141 cP, this is 705 timesmore water and 7050 times more than the viscosity of nitrogen. With theabove it is demonstrated the technological advantage of using thefoaming compositions objects of the present invention as foamingadditives under high pressure, 3500 psi (246 kg/cm²), high temperature(150° C.) and ultra-high salinity brines and high hardness.

TABLE 9 Share rate (1/s) Experimental Apparent Viscosity (cP) 74.2541.51 55.69 49.49 37.12 59.07 18.56 77.75 9.28 141.14 4.64 187.47d) Determination of Blocking Factor.

The test method is to evaluate the resistance factor or blocking factorthrough the use of the foam. For this evaluation, a matrix-fracturesystem consisting of a cylindrical core of Bedford limestone (matrix) of3.5 inch diameter, 10 cm (3.94 inch) in length and a longitudinal cut(fracture) was used, (FIG. 14). As part of a preliminary work to theevaluation of the use of foams, the flow for the matrix-fracture systemit was characterized. The objective of this stage was to determine thebehavior of the opening of the fracture according to the confiningpressure (overload).

EXPERIMENTAL EQUIPMENT

To characterize the matrix-fracture system was used an experimentalequipment whose detail is shown in FIG. 15. The rock core is mounted ona sleeve system to seal by confining pressure the outer surface of thecylinder, this sample holder Hassler type can apply confining pressureor of overload to the rock sample reducing the opening of thelongitudinal fracture to achieve different fracture permeabilities.

Then it described summarize the experimental methodology:

1. Determination of the weight of the rock-core sample clean and dry,corroborating dimensions, diameter and length.

2. Mounting of core with longitudinal cut in experimental cell (sampleholder type Hassler) for high pressure and temperature.

3. Installation of the experimental cell in displacement system.

4. Application of the confining pressure to seal the Viton sleeve of theexperimental cell against the porous media.

5. Application of vacuum to the system and the experimental cell for 30minutes.

6. Injection of formation water to achieve 100% of saturation in theporous media. This was corroborated by several cycles of pressing in at1000 psi (70 kg/cm²).

7 Determination of differential pressure variation for different VFR ofinjection and different confining pressures. Allow pressure equalizationfor each flow. The injected fluids respect the following order:

-   -   a. Injection of formation water (brine 2).    -   b. Displacement of formation water through the injection of        nitrogen gas (N₂).    -   c. Foam injection.    -   d. Displacement of the foam through the injected of nitrogen gas        (N₂).        8. Disassembly of the experimental cell and revision of the rock        sample.        9. Determination of the weight of the rock sample to 100% of        saturation conditions with water.        10. Interpretation of the experimental data to determine the        blocking factor generated. FIG. 16 shows a block diagram which        summarizes the methodology used.

Example 19

Was carried out the determination of the blocking factor using themultifunctional foaming composition 2, and the brine 2 whose compositionis shown in Example 14.

Determination of the Pressure Drop Along the Fracture.

a) With brine. Tests were made at different confining pressures; 1,000;1,500 and 2,500 psi (70, 105 and 176 Kg/cm²) at room temperature (22°C.) and back pressure injection (BPI=500 psi (35 kg/cm²)).

In FIG. 17 are shows the behavior of the pressure drop along thefracture when the brine 4 is injected, VFR and confining pressures.

b) With foam. The Foam generation was carried out with themultifunctional foaming composition 2 at a concentration of 0.2% in thebrine 4 and to generate the foam nitrogen gas was used.

In FIG. 18 are shows the pictures of foam generated and in the FIG. 19are shows the behavior of the pressure drop along the fracture when thebrine 4 is injected, VFR and confining pressures.

c) With nitrogen gas (N₂). Nitrogen gas is injected in order to displacethe fluid present in the core, whether these formation water (brine 4)or the foam generated by the foaming composition 2 of the presentinvention.

FIG. 20 shows the behavior of the pressure drop along to the fracturewhen nitrogen is injected to displace foam and brine, VFR to a confiningpressure of 2500 psi (176 Kg/cm²).

Comparing the pressure drop along the core with brine and foam can becalculate the blocking factor.

Determination of the Blocking Factor.

After injection of a fluid, it being this formation water (brine 4) orfoam, it is carried out a sweep with nitrogen gas.

The ease with which the nitrogen flows through the core depends on thefluid to move or sweep and can be estimated by measuring the pressuredrop.

The F_(b) blocking factor is calculated as follows:

$F_{b} = \frac{\Delta\; P_{{gas}\mspace{14mu}{to}\mspace{14mu}{displace}\mspace{14mu}{the}\mspace{11mu}{foam}}}{\Delta\; P_{{gas}\mspace{14mu}{to}\mspace{14mu}{displace}\mspace{14mu}{the}\mspace{14mu}{water}}}$

The results obtained for blocking factor showing in Table 10.

TABLE 10 Blockade factors to different gas injection rates. VFR (mL/min)5 10 15 Blocking factor 13.9 11.2 10.3II) Evaluation of the Wettability Modifying Properties.

The following examples will serve to demonstrate the use of the foamingcompositions object of the present invention as wettability modifiers.

For this evaluation, was carried out in four ways: a) Evaluation of oildetachment adsorbed on a rock to atmospheric conditions; b)Determination of spontaneous imbibition into small fragments of dolomitein Amott cells; c) Determination of spontaneous imbibition in limestonecores into cells Amott; d) Determination of spontaneous imbibition inlimestone cores in a glaze reactor of high temperature; e) Determinationof the change in contact angle at reservoir conditions; and, f)Determination of crude oil recovery factor by injecting foam into ashift test at reservoir conditions.

a) Evaluation of the Detachment of the Absorbed Oil on a Rock toAtmospheric Conditions and Static.

The test method consists of a procedure to observe how the oil adsorbedon a rock immersed in brine with high content of total dissolved solidsand divalent ions such as calcium and magnesium with or without presenceof chemical, to determine the time in which it is achieved detach asmall amount of oil in the system.

Elements Required for the Test:

-   -   Beakers of 50 milliliters.    -   Small fragments of dolomite, limestone or sandstone.    -   Camera.    -   Oil crude typical of carbonate reservoirs.    -   Brine.        Test Procedure        1. Prepare 100 ml of the aqueous solution (brine) to evaluate        the concentration of chemicals required in the test.        2. Place a small piece of rock (dolomite, limestone or        sandstone) of 2×2×1 cm of dimensions in a beaker of 50        milliliters.        3. Place carefully two drop of crude oil on the surface of the        small piece of rock.        4.—Allow the rock-oil system is balanced, giving a standing time        of 30 minutes.        5. Check if the surface of the rock is oil-wet.        6.—Add carefully 25 ml of the aqueous solution to evaluate to        the concentration of chemicals required in the test.

Ensure that the rock-oil system is completely immersed in the aqueoussolution to be evaluated.

7.—Observe the release of oil in the oil-rock-aqueous solution systemand leaving evidence of them through photographs.

8.—Determining the time at which the release of oil in the system due toexposure to the chemicals are begins.

9.—The duration of the test is one hour.

Example 20

Was carried out the evaluations of the release of oil in a rock/oil andbrine system to atmospheric and static conditions for themultifunctional foaming composition 2 at different concentrations. Ituses the brine 1 (whose composition is described in Example 11), rockplates composed of 99% of dolomite and 1% of limestone and oil whosecomposition is shown in Table 11.

TABLE 11 Fraction (wt %) Saturates 28.09 Aromatics 43.69 Resins 24.46Asphaltene 3.72

In FIGS. 21, 22 and 23 showing the detachment results of the oil usingthe multifunctional foaming composition 2 at different concentrations.The results reported in FIGS. 21, 22 and 23 show that themultifunctional foaming composition 2 is capable of releasing the oil inless than 1 hour of have contact with the oil adsorbed on the rock underambient conditions and high salinity brines as well as oils rich inasphaltenes.

With the above it is demonstrated the technological advantage of usingthe foaming compositions of the present invention as modifierswettability under temperature conditions, atmospheric pressure andultra-high salinity brines with high hardness.

b) Determination of Recovery Factor in Small Fragments of Carbonate Rockinto Amott Cells.

The test method consists in determine the oil recovery factor atdifferent temperatures, due to processes of spontaneous imbibition ofwater in small fragments of carbonate rock and/or cores with knownpermeabilities and porosities.

Elements Required for the Test:

-   -   Amott cells. (FIG. 24)    -   Recirculating of temperature controlled.    -   Small fragments of dolomite, limestone or sandstone.    -   Camera.    -   Typical oil crude of carbonate reservoirs.    -   Typical brine of the reservoirs that possess high salinities.    -   Supramolecular complex or chemical to evaluate.    -   Analytical balance.    -   Glass equipment of extraction (SOXHLET).    -   Volumetric Glassware.    -   Convection stove.        Test Procedures:        1) Submit to hydrocarbon extraction processes with different        organic solvents in a SOXHLET system to small fragments of rock        (dolomite, limestone or sandstone) coming from the reservoir for        which it is intended to conduct the study. The extraction        processes are performed continuously, sequenced and in reflux;        using as solvents: a) Hexane b) Xylene c) Chloroform, d)        Methanol, e) Hexane, f) Xylene g) Chloroform. The duration of        each extraction stage is one day and the total process time is 7        days.        2) Dry the small rock fragments in an oven at a temperature of        100° C. and record the weight after reaching a constant weight.        3) Put in touch the small fragments of rock with dead oil from        the site of interest, for 24 hours at the required temperature        and a pressure of 140±5 psi (10 kg/cm²) in a maturing cell.        4) Drain at room temperature and atmospheric pressure the small        fragments of impregnated rock with dead oil to note that there        is no longer dripping. The process of draining it lasts about 12        h and for this use is made of a wire mesh number 200.        5) Weigh the small rock fragments impregnated with dead oil and        obtain through a weight difference the amount of oil adsorbed by        the porous media.        6) Prepare 400 ml of aqueous solution (brine) to evaluate the        concentration of chemical required in the test.        7) Place 60 g of small fragments of rock impregnated with dead        oil in the Amott cell and carefully adds 350 ml of the chemical        to evaluate to the required concentration.        8) Increase the temperature of the system to which you want to        make the performance evaluation of the chemical or study sample        and maintain it for a period of time which is intended to        determine recovery factor under the conditions of temperature        and salinity.        9) Quantify the amount of oil produced due to processes of        spontaneous imbibition of water under the conditions of study        and determine the recovery factor according to the following        equation:

$\begin{matrix}{F_{r} = {\frac{A_{r}}{A_{omp}} \times 100}} & {{Equation}\mspace{14mu} 8}\end{matrix}$were:F_(r)=Recovery factor.A_(r)=Oil recovered.A_(omp)=Original oil adsorbed in the porous medium.

Example 21

Was carried out the evaluation of the full recovery factor at aconcentration of 0.2 Wt %, using as evidence the brine 1 described inexample 11, fragments of limestone and oil whose characteristics showingin Table 12, for a temperature of 90° C. and atmospheric pressure.

TABLE 12 Fraction Saturates (wt %) 13.4 Aromatics (wt %) 24.76 Resins(wt %) 51.01 Asphaltene (wt %) 10.44 Acid number (mg KOH/g) 1.83 Basicnumber (mg KOH/g) 2.12 Gravity API 18

In FIG. 25 showing the Amott cells and recovered oil and in FIG. 26showing a graph with the behavior of the recovery factor versus time forthe tested products. In Table 13 showing the results of the recoveryfactor accumulated in a time of 8 days at a temperature of 90° C.

TABLE 13 ACCUMULATED PRODUCT RECOVERY FACTOR (%) BRINE 1 4 Foamingcomposition of the patent 7 application Mx/a/2012/014187 Multifunctionalfoaming composition 1 15 Multifunctional foaming composition 2 20Multifunctional foaming composition 3 13 Multifunctional foamingcomposition 4 14 Multifunctional foaming composition 5 13Multifunctional foaming composition 7 11 Multifunctional foamingcomposition 9 22

The results show that the foaming compositions of the present inventionrecovered in more than three times the obtained by the brine 1 and morethan 2 times the obtained by the foaming composition of the patentapplication MX/a/2012/014187.

Example 22

Was carried out the evaluation of the recovery factor for themultifunctional foaming compositions 2 and moreover was evaluated thefoaming composition 9 in order to determine the effect of a zwitterionicliquid geminal, at a concentration of 0.2 Wt %, using as evidence thebrine 5 whose composition is described in Table 14, carbonate rockfragments, oil whose composition is shown in Table 15 and a temperaturerange of 80 to 100° C. In FIG. 27 are showing a graphic with thebehavior recovery factor with respects to the time for the testedproducts. In Table 16 are showing the results of the accumulatedrecovery factor for brine 5, the foaming composition of the patentapplication MX/a/2012/014187 and the foaming compositions 2 and 9.

TABLE 14 CONCENTRATION (mg/L) CATIONS Na⁺ 10906.47 Mg²⁺ 777.51 Ca²⁺2320.04 Fe²⁺ 0.1123 Ba²⁺ 29.79 ANIONS Cl⁻ 112602.68 SO₄ ²⁻ 75.06 HCO₃ ⁻941.89

TABLE 15 Fraction Saturates (wt %) 13.4 Aromatics (wt %) 24.76 Resins(wt %) 51.01 Asphaltene (wt %) 10.44 Acid number (mg KOH/gr) 1.83 Basicnumber (mg KOH/gr) 2.12 Gravity API 18

TABLE 16 ACCUMULATED RECOVERY PRODUC FACTOR (%) BRINE 5 3.1 Foamingcomposition of the 5.9 patent application Mx/a/2012/014187Multifunctional foaming 8.4 composition 2 Multifunctional foaming 12.4composition 9

The results show that the foaming compositions of the present inventionrecovered more than twice the obtained by the brine 5 and in to morethan 42% the obtained by the foaming composition of the patentapplication MX/a/2012/014187.

Example 23

Was carried out an evaluating of the recovery factor for themultifunctional foaming compositions 2 and 9, at a concentration of 0.2Wt %, using as evidence the brine 6 whose composition is described inTable 17, carbonate rock fragments, oil whose composition is shown inTable 18 and in a temperature range of 80 to 100° C.

TABLE 17 CONCENTRTION (mg/L) CATIONS Na⁺ 10906.47 Mg²⁺ 777.51 Ca²⁺2320.04 Fe²⁺ 0.1123 Ba²⁺ 29.79 ANIONS Cl⁻ 112602.68 SO₄ ²⁻ 75.06 HCO₃ ⁻941.89

TABLE 18 Fraction Poza Rica Saturated (wt %) 30.68 Aromatic (wt %) 28.62Resins (wt %) 39.35 Asphaltene (wt %) 1.32 Acid number (mg KOH/gr) 0.20Basic number (mg KOH/gr) 1.7

In FIG. 28 are showing a graph with the behavior of the recovery factorwith respect to time for the tested products.

In Table 19 are showing the accumulated recovery factor results for thebrine 6 shown, the foaming composition of the patent applicationMX/a/2012/014187 and the foaming compositions 2 and 9.

TABLE 19 ACCUMULATED RECOVERY PRODUCT FACTOR (%) BRINE 6 0.5 Foamingcomposition of the 2.7 patent application Mx/a/2012/014187Multifunctional foaming 8.3 Composition 2 Multifunctional foaming 10.8Composition 9

The results show that the foaming compositions of the present inventionrecovered more than sixteen times that the obtained by the brine 6 andmore than 2.5 times that the obtained by the foaming composition of thepatent application MX/a/2012/014187. With the above is demonstrated thetechnological advantage of using the foaming compositions of the presentinvention as modifiers of wettability under atmospheric pressure,temperature range of 80 to 100° C., high-salinity and high-hardnessbrines, oil and rock fragments of different compositions.

c) Determination of Recovery Factor with Limestone Cores into AmottCells.

The test method consists in determining the oil recovery factor atdifferent temperatures, due to processes of spontaneous imbibition ofwater in small carbonate rock cores with permeabilities- andporosities-known.

Elements Required for the Test:

-   -   Amott cells.    -   Recirculating of temperature controlled.    -   limestone core diameter 3.81 cm×7 cm long and its permeabilities        and porosities known.    -   Camera.    -   Typical crude oil of carbonate reservoirs.    -   Typical brine of the reservoir that possess high salinities.    -   Supramolecular complex or chemical to evaluate.    -   Analytical balance.    -   Glass equipment of extraction (SOXHLET).    -   Volumetric Glassware.    -   Convection oven.        Test Procedures:        1) To submit to hydrocarbon extraction processes with different        organic solvents in a SOXHLET system the carbonated cores        (dolomite or limestone) or sandstone from the reservoir for        which it is intended to conduct the study. The extraction        processes are performed continuously, sequenced and reflux;        using as solvents: a) Xylene b) Chloroform, c) Methanol, d)        Xylene e) Chloroform, f) Methanol) and g) Xylene. The duration        time of each extraction stage is one day and the total process        time is 7 days.        2) Determining the absolute permeability to helium for the        cores, and its effective porosity        3) Dry cores in an oven at 100° C. and record the weight after        reaching a constant weight.        4) Contacting the cores with dead oil from the reservoir of        interest, for 5 days at the temperature of interest and a        pressure of 140±5 lbs in an aging cell.        5) Drain at room temperature and atmospheric pressure the        impregnated cores with dead oil to note that there is no        dripping. The runoff process takes about 12 h and for this are        using a wire mesh of 200.        6) Weigh the cores impregnated with dead oil and obtain the        weigh difference by the amount of oil adsorbed through the        porous media.        7) Prepare 500 ml of aqueous solution (brine) to evaluate the        concentration of chemical required in the test.        8) Placing the core impregnated with the dead oil in to the        Amott cell and carefully add 350 milliliters of chemical to        evaluate to the required concentration.        9) Increase the temperature of the system to the temperature to        which it is intended make the evaluation of the chemical perform        or sample in study and maintain it for a period of time which is        intended to determine the recovery factor under the temperature        and salinity conditions.        10) Quantify the amount of oil produced due to processes of        spontaneous imbibition of water under the conditions of study        and determine the recovery factor according to the following        equation:

$\begin{matrix}{F_{r} = {\frac{A_{r}}{A_{omp}} \times 100}} & {{Equation}\mspace{11mu} 9}\end{matrix}$where:F_(r)=Recovery FactorA_(r)=Oil recoveredA_(omp)=Original oil adsorbed in the porous medium.

Example 24

Was carried out the evaluating of the recovery factor for themultifunctional foaming composition 2 as well as the multifunctionalfoaming composition 9 in order to evaluate the effect of thezwitterionic liquid in the composition at a concentration of 0.2 Wt %,using as evidence the brine 4 whose composition is shown in example 14,crude oil whose composition are showing in Table 20 and limestone coresat a temperature of 90° C.

In Tables 20 and 21 are showing the oil and core of limestonecharacteristics used.

TABLE 20 Absolute Core Measures permeability to Core Porosity (cm)helium (mD) (%) 3.81 × 7 120 19

TABLE 21 Fraction (wt %) Saturates 40.91 Aromatics 36.13 Resins 22.30Asphaltene 0.20

In FIG. 29 are showing the clean core and during the test, as well asthe recovery of oil. In FIG. 30 are showing a graph with the behavior ofthe recovery factor with respect to time for the tested products. InTable 22 are showing the results of the recovery factors for the foamingcompositions 2 and 9 of the present invention at a concentration of 0.2Wt %. The results shown in Table 22 indicate that the multifunctionalfoaming compositions 2 and 9 recover 9 times more of oil with respect tothe recovery which was obtained using only the brine 4.

TABLE 22 Recovery Factor PRODUCT (%) BRINE 4 2.5 Multifunctional foaming20 Composition 2 Multifunctional foaming 25 Composition 9

With respect to the multifunctional foaming composition 9, recovered 5%more oil compared to composition 2. With the above it is demonstratedthe technological advantage of using the foaming compositions of thepresent invention as well as the zwitterionic liquids use into thefoaming compositions as modifiers of wettability under atmosphericpressure at a temperature of 90° C., ultrahigh salinity and highhardness brine, oil and rock-core of the carbonate type.

d) Determination of Recovery Factor in a Glaze Reactor of HighTemperature.

The equipment consists of a glaze reactor where is introduced a corepreviously oil impregnated that comes into contact with aqueous mediumwith chemical. The experimental conditions are as follows:

-   -   Experimental pressure: 140 psi (10 kg/cm²)    -   Experimental Temperature: 150° C.    -   Limestone core 7×3.8 cm.    -   Brine 4    -   Injection gas: Nitrogen        Procedure:        Elements Required for Testing:    -   Glaze reactor    -   Recirculating of temperature controlled.    -   Limestone core of permeabilities and porosities known.    -   Camera.    -   Typical crude oil of carbonate reservoirs.    -   Typical brine of the reservoir that possess ultra-high        salinities.    -   Supramolecular complex or chemical to evaluate.    -   Analytical balance.    -   Glass equipment of extraction (SOXHLET).    -   Volumetric Glassware.    -   Convection oven.        Test Procedures:        1) To submit to hydrocarbon extraction processes with different        organic solvents in a SOXHLET system to the cores carbonated        rock (dolomite or limestone) or sandstone from the reservoir for        which it is intended to conduct the study. The extraction        processes are performed continuously, sequenced and reflux;        using as solvents: a) Xylene b) Chloroform, c) Methanol, d)        Xylene e) Chloroform, f) Methanol) and g) Xylene. The duration        of each extraction stage is one day and the total process time        is 7 days.        2) Determining the absolute permeability to helium of the cores        as well as its effective porosity.        3) Dry cores in an oven at 100° C. and record the weight after        reaching a constant weight.        4) Put in contact the cores with dead oil from the reservoir of        interest, for 5 days at the temperature of interest and a        pressure of 140±5 psi (10 kg/cm*) in an aging cell.        5) Drain at room temperature and atmospheric pressure the        impregnated cores with dead oil to note that there is no        dripping. The runoff process takes about 12 h and for this using        a wire mesh of number 200.        6) Weigh the impregnated cores with dead oil and obtain through        weigh difference the amount of oil adsorbed in the porous media.        7) Prepare 500 mL of aqueous solution (brine) to evaluate to the        concentration of required chemical in the test.        8) Placing the impregnated core with the dead oil in the glaze        reactor and carefully add 500 mL of chemical to evaluate to the        required concentration.        9) It is pressurized with nitrogen up to 140 psi (10 kg/cm²).        10) Increase the system temperature to the temperature to which        it is intended to make the performance evaluation of the        chemical or sample in study and maintain it for a period of time        which is intended to determine the recovery factor under the        conditions of temperature and salinity.        11) Quantify the amount of produced oil due to processes of        spontaneous imbibition of water under the conditions of study        and determine the recovery factor according to the following        equation:

$\begin{matrix}{F_{r} = {\frac{A_{r}}{A_{omp}} \times 100}} & {{Equation}\mspace{11mu} 10}\end{matrix}$where:F_(r)=Recovery FactorA_(r)=Oil recoveredA_(omp)=Original oil adsorbed in the porous medium.

The equipment used is shown in FIG. 31.

Example 25

It was carried out the evaluation of the recovery factor for the foamingcomposition 2 at a concentration of 0.2 Wt %, using as evidence thebrine 4 whose composition is shown in example 14, crude oil whosecomposition is shown in Table 23 and limestone cores at a temperature of90° C. In Tables 23 and 24 are showing the characteristic oil andlimestone core used.

TABLE 23 Absolute permeability Core Measures (cm) to helium (mD) Coreporosity (%) 3.81 × 7 118 20

Fraction (wt %) Saturates 40.91 Aromatics 36.13 Resins 22.30 Asphaltene0.20

In FIG. 32 are showing the equipment used and the core during the test.In Table 25 are showing the results of the total recovery factor formultifunctional foaming composition 2 of the present invention at aconcentration of 0.2 Wt %.

TABLE 25 PRODUCT RECOVERY FACTOR (%) BRINE 4 10.5 Multifunctionalfoaming composition 2 39.1

The results shown in Table 25 indicate that the multifunctional foamingcomposition 2 recovers almost 4 times more oil with respect to therecovery that was obtained using only the brine 4. With the above isdemonstrated the technological advantage of using the foamingcompositions of the present invention as modifiers of wetting under hightemperature conditions (150° C.) and brine of ultra-high salinity andhigh hardness, oil and rock core type carbonated.

e) Determination of the Change in Contact Angle at Reservoir Conditions.

Was carried out the determination of the change of contact angle atreservoir conditions using a high pressure cell and high temperature.

Example 26

It is determined the change of contact angle generated by themultifunctional foaming composition 2 to a pressure of 3820 psi (269Kg/cm²) and a temperature of 132° C. using an oil whose composition isshown in Table 26 and the brine 3 whose composition is shown in Example14.

TABLE 26 Fraction Saturates (wt %) 31.88 Aromatics (wt %) 48.84 Resins(wt %) 18.81 Asphaltene (wt %) 0.38 Acid number (mg KOH/gr) 0.29 Basicnumber (mg KOH/gr) 1.33

In FIG. 33 are showing the change in contact angle generated by themultifunctional foaming composition 2 to reservoir conditions. Thefoaming composition change the contact angle of oil, of 0° to 141.7° ofa fragment of carbonate rock, this result indicates that themultifunctional foaming composition 2 is able to favorably change thewettability at reservoir conditions and high salinity.

f) Determination of the Recovery Factor of Crude Oil by Injecting Foaminto a Displacement Test at Reservoir Conditions.

To perform the displacement test where use carbonate rock cores,naturally fractured and were accommodated in an experimental cellforming a stacking (FIG. 34) which was with a vertical annular fracturebetween each of the fragments (with a thickness of 1.0 mm), between eachcore a filter paper is placed so that there is continuity capillary of amedium to another and the rock cores are between two diffusers, one ateach end. With the installed system is carried out the water and oilsaturation to reproduce the initial conditions of saturation of thefluids. In FIG. 35 the laboratory cell and the stacking of the cores areshown.

Experimental Methodology

The experiment consists of carrying out a foam injection in a stack ofrock cores at reservoir conditions to estimate the recovery factor.

This test is performed by the following steps:

First Stage. Oil Recovery by Pressure Reduction.

This part of the experiment simulates the behavior of primary recoveryfollowing the trend of the decrease in reservoir pressure, through thisprocess is carried out a recovery of oil from the bottom of the cell.The experimental start with the stabilized system at reservoirconditions (initial reservoir conditions), then the oil recovery processbegins by pressure reduction of the system, starting from an initialreservoir pressure to a final pressure.

Pressure Maintenance.

Once obtained the first stage of the oil recovery by pressure reduction,this pressure reached in the system remains constant through a systemcalled back pressure regulator, which prevents that the pressure can beraised and/or reduce of the desired value to continue with theexperimentation.

Foam Injection in the Stack.

After reaching the desired pressure in the previous stage, the next stepis to inject the foam. The foam was generated within the container orheating oven which also contains the displacement cell.

The foam injection is performed in two stages: The first stage involvesthe injection of a soaking pothole with wet foam, i.e. foam of poorquality. For this experiment was 80% of surfactant and 20% of gas. Thispothole is small. The second stage is the injection of dry foam orhigher quality and the used was of 80% by 20% of liquid. This pothole islarge and with it ends the test.

Analysis of the Experiment and Calculation of the Recovery Factor.

Once it concludes with the experiments, we proceed to conduct averification of the obtained volumes of oil and water to account all thesamples to be collected and separated according to the type of fluid.Once you have counted the recovered fluids, it is counted with thenecessary information to make the interpretation of the behavior of therecovery factor, so that you can generate graphics of volume ofproduction versus time, recovery factor versus time, production ofwater, gas, etc. They are also generated Tables and you can be obtainedphotographic images of the fluid samples obtained, rock samples, etc.

Example 27

It was carried out the determination of the recovery factor of crude oilthrough the injection of the generated foam by the multifunctionalfoaming composition 2 of this invention in a displacement test atreservoir conditions.

Test Characteristics.

The oil recovery process and the injected volumes of fluid were asfollows (volumetric flow rate of injection test=5 ml/h):

-   -   Recovery of oil by reducing pressure of 4762 psi (335 kg/cm²) to        2914 psi (205 kg/cm²).    -   Injection of wet foam, pothole of approx. 5.6% of Vp *    -   Injection of dry foam, pothole of 47.2% of Vp *    -   Injection of surfactant, pothole 10% of Vp *    -   The pore volume (Vp) total of the system, i.e. including the        annular fracture, and the porosity of the fragments.        Oil Recovery by Pressure Reduction.

This part of the experiment simulates the behavior of primary recoveryfollowing the trend of the decrease in reservoir pressure, through thisprocess is carried out a recovery of oil from the bottom of the cell.The experimental initiation is with the system stabilized at reservoirconditions (initial reservoir conditions), then the oil recovery processbegins by pressure reduction of the system, starting from an initialreservoir pressure of approx. 335 Kg/cm² (4760 psi) to a final pressureof 205 Kg/cm² (2911 psi), considered as the pressure at which areservoir could be found after a primary recovery and the experiment wascarried out at a temperature of 160° C. In FIG. 36 are showing the oilrecovery with respect to time while the system reduce the pressure.

Foam Injection in the Stack.

Reaching the desired pressure in the previous stage, the next step isfoam injection. The foam is generated inside a cell of high pressure andtemperature and immediately is injected to the cell that contains thestack. The foam injection is performed in two stages: the first stageinvolves the injection of a soaking pothole with a wet foam, i.e. a foamof poor quality. For this experiment was 80% of surfactant and 20% ofgas. This pothole is small regularly. The second stage is the injectionof dry foam or higher quality and the used was of 80% by 20% liquid.This pothole is large and with it ends the test. In FIG. 37 it presentsthe oil recovery with respect to the time while are injecting the foamat the top of the system. Once it concludes the experiments, we proceedto conduct a verification of the obtained volumes of oil and water toaccount all the samples to be collected and separated according to thetype of fluid. In Table 27 are showing the recovery factors obtainedduring the displacement test by going reducing the pressure in thesystem and inject the formed foam with multifunctional foamingcomposition 2 of the present invention.

TABLE 27 Recovery factor obtained in the displacement test. Cumulativerecovery factor (%) pressure reduction Foam injection 9.19 79.03

With the above it is demonstrated the technological advantage of usingthe foaming compositions of the present invention to increase therecovery factor under high temperature and high salinity conditions.

III) Determination of Adsorption on Mineral of Carbonated Type.

The methodology consists in the quantitative determination of adsorptionby High-performance liquid chromatography (HPLC) of a chemical incontact with mineral of carbonated type.

Procedure:

-   -   a) The rock (Limestone) is fragmented into 1 m²/g.    -   b) Small fragments of rock are washed sequentially and reflux        temperature of the following solvents: a) Hexane b) Toluene c)        Chloroform and d) Methanol.    -   c) Rock fragments are dried in an oven at a temperature of        100° C. until reaching a weight constant.    -   d) Solution of 5,000 ppm are prepared of the chemical in the        desired brine performing dilutions with the same solvent to        concentrations of 4,000; 3,000; 2,000; 1,000; 500; 200 and 100        ppm.    -   e) It weighs 4 g of rock were adding 20 ml of different        concentrations of the chemical prepared.    -   f) The dissolution/rock/chemical is stirred for 12 h at room        temperature.    -   g) Finished the stirring time the sample is filtered on a glass        funnel with filter of 2 μm followed by a 0.5 μm filter.    -   h) Subsequently it conducted an injection of 15 μl into the HPLC        for each prepared concentration.

Example 28

It was carried out the determination of the adsorption ofmultifunctional foaming composition 2 of the present invention onlimestone at a concentration of 0.2 wt % (2,000 ppm) using the brine 2whose characteristics are presented in Example 14. The adsorption resultfor the foaming composition 2 for a concentration of 2,000 ppm was 4.35mg of foaming composition 2 per gram of rock. In order to determine theeffect from the corrosion to use the foaming compositions of the presentinvention in conjunction with ultra-high salinity brines, it wasconducted to determine the efficiency of corrosion inhibition asdescribed below.

IV) Determination of the Efficiency of Corrosion Inhibition.

It is a gravimetric test commonly called dynamic wheel (Wheel test)simulating the typical corrosive environment of oil production. It is adynamic process developed for fluids (oil, water and inhibitor (foamingcomposition)).

Equipment and Reagents for Test

a) Dynamic evaluation of corrosion inhibitors with temperaturecontroller, stirrer speed of 30 rpm and with capacity for 52 bottles of180 mL.

b) Bottles of 200 ml capacity.

c) Carbon steel coupons of SAE 1010, of dimensions 1″×0.5″×0.010″.

d) Glass equipment for the preparation of corrosive medium. Thisconsists of a glass reactor of 2 L of capacity equipped with a coolingbath, mechanical stirrer, sparger for gas (nitrogen and hydrogensulfide) possess an outlet connected to two traps in series connected(the first with hydroxide sodium in flakes and the second with anothersolution of sodium hydroxide at 20%) in order that the hydrogen sulfidedoes not contaminate the environment.e) Potentiometer for Measuring pH.

Example 29

It was carried out the evaluation of the efficiency as corrosioninhibitor for the foaming composition 2 at a concentration of 0.2 Wt %(2,000 ppm), using as test medium a mixture of brine 1 and 3 describedin Examples 11 and 14, in a 3:1 ratio respectively and crude oil whosecomposition is described in Table 28.

TABLE 28 Fraction (Wt %) Saturates 40.91 Aromatics 36.13 Resins 22.30Asphaltene 0.20

The test conditions are shown in Table 29.

TABLE 29 Temperature 70° C. Aqueous medium Mixture of brines with 600+/− 50 ppm de H₂S Test duration 46 h Organic medium Crude oil Volumeratio of brine/organic medium 90/10 Test volume 180 mL pH of the medium4.8 Witness corrosion (metal coupons) Steel SAE 1010Obtaining of Results.

The difference in weight of the coupons before and after being exposedto the corrosive environment for 46 h, is a direct indication of lostmetal due to corrosion. The efficiency as a corrosion inhibitor isestablished by comparing the corrosion rates of the control or targetwith the velocities or target having a certain concentration ofinhibitor product as shown in the following formula:

$\begin{matrix}{{\%\mspace{14mu}{of}\mspace{14mu}{efficiency}} = {\frac{V_{o} - V}{V_{o}} \times 100}} & {{Equation}\mspace{14mu} 11}\end{matrix}$where:V_(o)=Corrosion rate of the target coupon (Reference).V=speed of corrosion of the coupon with corrosion inhibitor.In Table 30 are showing the results for the foaming compositions 2 and9, at a concentration of 2,000 ppm.

In FIG. 38 are showing the metal coupons used in the test.

TABLE 30 Corrosion rate Efficiency Produc (mpy) (%) Reference 37.5 —Multifunctional foming 2.7 92.5 composition 2 *mpy: milli-inch per year

The results show that the foaming compositions 2 and 9 of the presentinvention possess anti-corrosive properties in acid- and high salinityenvironments, characteristics of pipelines of crude oil production.Moreover, in order to determine what would be the effect of have in thefoaming composition a zwitterionic liquid were evaluated the foamingcomposition 9 under the same conditions described in this example. InTable 31 are showing the result of the efficiency of corrosioninhibition for foaming composition 9.

TABLE 31 Corrosion rate Efficiency Product (mpy) (%) Reference 37.5 —Multifunctional foming 1.9 96.5 composition 9 *mpy: milli-inch per year

The above results show that the multifunctional foaming composition 9increased by by 4% more the efficiency as a corrosion inhibitor of themultifunctional foaming composition 2, in acids and high salinityenvironments, characteristics of production pipelines of crude oil andproduction rigs.

V) Experimental Evaluation of the Anti-Scale Properties and Dispersantsof Mineral Salts.

The evaluation of anti-scale ability of foaming compositions of thepresent invention was performed using four different tests:

a) Determination of the inhibition of mineral scale of calcium sulfateas much as qualitative as well as quantitative, b) Determination of thescale inhibition of calcium carbonate, calcium sulfates, barium andstrontium,

c) Determination of the inhibition of mineral scale at reservoirconditions (high temperature and high pressure) and d) Determination ofdistortion and crystal modification of calcium-sulfate and -carbonate byscanning electron microscopy.

a) Determination of Mineral Scale Inhibition of Calcium Sulfate.

In the Case of Calcium Sulphate.

The method consists in mixing two solutions to induce the formation ofcalcium sulfate.

1. Are preparing two solutions that containing calcium and sulphate ionsrespectively.

-   -   a) The solution containing calcium ions, containing: 7.5 g/L of        NaCl+11.1 g/L of CaCl₂.2H₂O.    -   b) The solution containing sulfate ions: containing: 7.5 g/L        NaCl+10.66 g/L of Na₂SO₄.        2. Are prepare the desired concentration of inhibitor in the        solution containing the sulfate ions.        3. Are mixed 50 ml of each one of the solutions and the desired        concentration of inhibitor and poured all in a sealed flask of        250 ml.        4. Are introduced the flasks in an oven for 24 h at a constant        temperature of 70° C.        5. After 24 h qualitatively are determined if they were formed        or not calcium sulfate crystals.        6. To determine quantitatively, after 24 h are allowed to cool        the flasks to room temperature. Are filtered the solids that        they have formed and a sample of 1 ml is taken and is completed        with 10 ml using ultrapure water.        7. The solution was analyzed by inductively coupled plasma        (ICP), in order to obtain the remaining calcium concentrations        of ion in the solution.

A control is prepared containing only the amount of calcium ions presentin the target. The percent of inhibition was calculated with thefollowing expression (1):

$\begin{matrix}{{\%\mspace{14mu}{Inhibition}} = {\frac{{Ca}_{SAP}^{+ 2} - {Ca}_{RAP}^{+ 2}}{{Ca}_{Tg}^{+ 2} - {Ca}_{RAP}^{+ 2}} \times 100}} & {{Equation}\mspace{14mu} 12}\end{matrix}$Were:SAP=sample after precipitationRAP=Reference after precipitationTg=Target

Example 30

It was carried out the qualitative determination of the inhibitorycapacity of calcium sulfate scale for the multifunctional foamingcompositions 1, 2 and 3. Coming up next are shown in Table 32 theresults at a concentration of 2,000 ppm of the foaming compositions 1, 2and 3.

TABLE 32 Results of the inhibition of calcium sulfate Product Crystalformation Reference Yes, a great quantity Multifunctional foaming Littleamount Composition 1 Multifunctional foaming No formation Composition 2Multifunctional foaming No formation Composition 3

In FIG. 39 are showing the vials used in the test.

Example 31

It was carried out the determination of the inhibitory capacity of scaleof the calcium sulfate for the multifunctional foaming compositions 2and 9. Coming up next are shown in Table 33 the results at differentconcentrations for the compositions 2 and 9.

TABLE 33 Results of the inhibition of calcium sulfate Calcium ProductConcentration concentration (ppm) Efficiency (%) Control Solution — 1510— Reference — 1017 0 Foming 1000 1509 99.8 composition 2 1500 1508 99.52000 1508 99.5 Foming 1000 1503 98.6 composition 9 1500 1500 98.0 20001476 93.1b) Determination of the Inhibition of Calcium Carbonate, CalciumSulfates, Barium and Strontium Scales.

This test involves mixing 2 incompatible water (injectionwater-formation water) in order to induce precipitation of inorganicsalts of calcium carbonate, sulfates of calcium, strontium and barium.Such salts are the main problem in oil extraction operations offshore.The methodology is the follows:

1. Are prepare 2 brines whose compositions are described in Table 34 andcontaining the calcium, strontium, barium, sulfate and bicarbonate ions:

2. Are prepare the desired inhibitor concentration in the brine A.

3. Are mixed 5 ml of each one of the briens A and B and the desiredconcentration of inhibitor and poured all in a closed tube of 25 mL andis stirred.

4. System turbidity is measured.

TABLE 34 Compositions of brines used. Sal Brine A (ppm) Brine B (ppm)NaCl 101564 3966 KCl 4157 147 MgCl₂ 26031 286 CaCl₂ 119811 833 SrCl₂2282 — BaCl₂ 1832 — Na₂SO₄ — 1874 NaHCO₃ — 260 Na₂CO₃ — 4

Example 32

With the purpose of determining the effect of the foaming compositionsderived from the present invention on a system that containing a highconcentration of calcium, barium, strontium, sulphate and bicarbonateions, the foaming composition 2 were evaluated in the brine mixture Aand B. Coming up next, in Table 35 are showing the results of turbidityin NTU (nephelometric units) as from the mixture of brine withoutchemical and the brine mix with the multifunctional foaming composition2.

TABLE 35 Table 35. Results of turbidity in the scale inhibition of:CaCO₃, CaSO₄, BaSO₄ and SrSO₄. Turbidity to Turbidity to 1,000 ppm 2,000ppm Produc (NTU) (NTU) Brine mixture A y B <1000 <1000 Foamingcomposition 2 22.1 16.2c) Determination of the Inhibition of Mineral Scale at ReservoirConditions (High Pressure and High Temperature) Characteristics of OilFields.

The evaluation as mineral scale inhibitor takes place in a mixture oftwo incompatible brines under reservoir conditions (high pressure andhigh temperature).

Assessment Methodology.

1.—Clean the equipment to be used:

-   -   peephole    -   BPR (back pressure regulator)    -   Transfer cylinder        2. Monitoring sensors are calibrated:    -   Pressure    -   Temperature        3. Arm the system.        4.—The water mixture is injected with and without product to the        required pressure.        5. The temperature is raised to the required condition and the        pressure is maintained by the BPR        6. The system is isolated and allowed monitor the pressure and        temperature.        7. Are taken photographic images during test to observe their        behavior and the possible formation of crystals.

The system for high pressure and high temperature used for performingthe determinations of inhibiting mineral scale at reservoir conditions(high pressure and high temperature) characteristics of oilfieldconsists of injection pumps, transfer cylinders, back pressureregulator, temperature control system, pressure monitoring system,digital camera and experimental cell.

Example 33

It was carried out the evaluation as mineral scale inhibitor of themultifunctional foaming composition 2 of this invention, which wasdissolved in a mixture of two incompatible brines (brines 7 and 8) underreservoir conditions (high pressure, high temperature). In Tables 36 and37 are showing the compositions of the brines used in the experiment.

TABLE 36 Compositions of the brines. Brine 7 Brine 8 mg/L mg/L CationsSodium 11742.09 101894 Calcium 448 24709.6 Magnesium 1288.43 341.9 Iron0.1 0.01 Barium — 23.91 Strontium 7.84 1417 Anions chlorides 19900112106 Sulfates 3650 145.9 Carbonates 13.12 0 Bicarbonates 84.18 145.18

TABLE 37 Hardness and salinity of the brines. Brine7 Brine 8 (mg/L)(mg/L) Total hardness, as CaCO₃ 6420 63181 Calcium hardness, as CaCO₃1120 61774 Magnesium hardness, as 5300 1407 CaCO₃ Salinity as NaCl 32804214000Test Conditions

-   -   Temperature: 163° C.    -   Pressure: 5,500 psi (387 Kg/cm²)

The water were mixed in a ratio of 3:1, (brine 7/brine 8)

Results

The test duration was about of 48 h, at time in which the systemconditions were kept constant in a temperature of 163° C. and 5,500 psi(387 Kg/cm²) of pressure. During this time, the system behavior ismonitored and photographic images were taken to evaluate the presence orformation of mineral precipitates.

In FIG. 40 are showing the photographic images for: a) Mixture offormation water+sea water without chemical at the start of the test, b)mixture of formation water+sea water with crystals after 4 h of startthe proof, c) mixture of formation water+sea water with the foamingcomposition 2 at the start the test and d) mixture of formationwater+sea water with the foaming composition 2 without the presence ofcrystals after 48 h of started the test. Making a comparison between theimage taken in the initial condition and the taken at different timesunder the same conditions of pressure and temperature, no precipitateminerals formation is observed, so that the performance as a scaleinhibitor for the foaming composition 2 is checked at conditions of highsalinity, high pressure and high temperature.

d) Determination by Scanning Electron Microscopy the Distortion andCrystal Modification of Sulfate and Calcium Carbonate.

The mineral scale deposited on the rock and that obstructing theporosity of the reservoir may be distorted or modified with the use ofchemicals in order to detach them from the rock and disperse formingsmaller particles and that can be removed with the flow.

In the case of calcium sulphate, the methodology is as follows: thesolutions that containing the calcium and sulfate ions are:

-   -   a) The solution containing calcium ions, contains 7.5 g/L        NaCl+2.22 g/L of CaCl₂.2H₂O.    -   b) The solution containing sulfate ions: contains 7.5 g/L        NaCl+21.32 g/L of Na₂SO₄.        1. Are prepared the desired concentration of chemical in the        solution that containing the sulfate ions.        2. Are mixed 5 ml of each of the solutions and the desired        concentration of inhibitor and poured all in a sealed tube of 25        mL.        3. The tubes were placed in an oven for 24 h at a constant        temperature of 70° C.        4. After 24 h the bottles are allowed to cool to room        temperature without allowing it to exceed 2 h. The solids that        have been formed are filtered.        5. The solids formed in the tubes are analyzed and their        morphology was observed by scanning electron microscopy (SEM).

In the case of calcium carbonate, the methodology is as follows: Thesolutions that containing the calcium and bicarbonate ions are:

a) Solution containing calcium ions: 12.15 g/L CaCl₂.2H₂O, 3.68 g/LMgCl₂.6H₂O and 33 g/L of NaCl.

b) Solution containing bicarbonate ions: 7.36 g/L NaHCO₃ and 33 g/L ofNaCl.

-   -   1. Are preparing the desired concentration of chemical in the        solution containing the sulfate ions.    -   2. Are mixed 5 ml of each one of the solutions and the desired        concentration of inhibitor and poured all in a sealed tube of 25        mL.    -   3. The tubes were placed in an oven for 24 h at a constant        temperature of 70° C.    -   4. After 24 h the bottles are allowed to cool to room        temperature without allowing it to exceed 2 h. The solids that        have formed are filtered.    -   5. The solids formed in the tubes are analyzed and their        morphology was observed by scanning electron microscopy (SEM).

Example 34

With the purpose of determining the effect of the foaming compositionsderivatives of the present invention on calcium sulphate crystals, themultifunctional foaming composition 2 was evaluated using two brineswith high concentrations of calcium and sulphate ions. In FIG. 41 areshowing the images and compositions of the crystals formed from mixingof the solutions shown for: a) without chemical and b) with 2,000 ppm ofthe foaming composition 2. Note that it is possible observe clearly howthe foaming composition 2, fragments and distorts the calcium sulfatecrystals, thereby inhibiting the growth of more-larger crystals.

Example 35

With the purpose of determine the effect of the foaming compositionsderivatives of the present invention on calcium carbonate crystals, themultifunctional foaming composition 2 was evaluated using two brineswith high concentrations of calcium and bicarbonate ions.

In FIG. 42 are showing the images and compositions of the formedcrystals from: a) The mixture of the solutions without chemical and b)mixing with 2,000 ppm of the foaming composition 2. From the Images itcan be clearly seen as the foaming composition 2, fragment and distortscalcium carbonate crystals, thereby inhibiting the growth of crystals.

Assessment of the Acute Toxicity with Artemia Franciscana.

This method is applicable for evaluation of acute toxicity in water andwater-soluble substances. In freshwater bodies, industrial and municipalwastewater, agricultural runoff and pure substances or combined orleachate and solubilize fraction in soils and sediments. Thedetermination of the acute toxicity was carried out through the Mexicanstandard NMX-AA-087-SCFI-2010, which establishes the method formeasuring the acute toxicity using the organism named Artemiafranciscana.

Example 36

It was carried out the toxicity determination of the foaming composition2 of the present invention through the Mexican standardNMX-AA-110-1995-SCFI, which establishes the method for measuringtoxicity using the organism named “Artemia franciscana Kellogg”(Crustacea—Anostraca) and the results are shown in Table 38.

TABLE 38 Toxicity of the multifunctional foaming composition 2. CE₅₀chemicals (ppm) *Toxicity Category Multifunctional foaming 118.38Particularly nontoxic composition 2 111.54 Particularly nontoxic 105.67Particularly nontoxic Average 111.86 Particularly nontoxic*Concentration range in ppm, classification, category 5: 0.01-0.10,extremely toxic; 4: 0.1-1.0, highly toxic; 3: 1-10, moderately toxic; 2:10-100, slightly toxic; 1: 100-1000, and particularly nontoxic 0 > 1000,nontoxic. ^(a)Toxicity category (UK) CNS for applying chemicals used inthe production of hydrocarbons in the North Sea.

The result of acute toxicity indicates the foaming composition 2 that isparticularly nontoxic to the organism Artemia franciscana.

Added to the above and based to the Mexican standard NRF-005-PEMEX-2009where it is established that so they can be used chemicals in the oilindustry which states that they can be used chemicals in the oilindustry must be comply the following environmental criteria. For marineenvironments, using the microorganism Artemia franciscana the limit intoxicity units (UT), should not exceed 2. The toxicity units (UT) arecomputed through the value LC₅₀ resulting from the toxicity test, fromthe following relation:

$\begin{matrix}{{UT} = {\frac{1}{{CL}_{50}} \times 100}} & {{Equation}\mspace{14mu} 13}\end{matrix}$where:UT=Acute Toxicity UnitsCL₅₀=Concentration of inhibitor (in mg/L which causes 50% mortality ofexposed organisms).

Therefore, the multifunctional foaming composition 2 of this inventionpossess a UT=0.89, so passing the Mexican standard NRF-005-PEMEX-2009and can be used in equipment and pipeline of the oil and chemicalindustry that using sea water or formation water oil reservoirs and thatare installed offshore.

With the above it is demonstrated the technological advantage of usingthe multifunctional foaming compositions of the present invention, dueto exhibit foaming properties of high performance, wettability modifier,anti-corrosive and anti-scale to be supplied in ultra-high salinitybrines and in acids environments characteristic of crude oil productionpipelines. Added to the above such compositions are classifiedparticularly as not toxic.

The invention claimed is:
 1. A multifunctional foaming composition,characterized by the combination of supramolecular complexes derivedfrom the interaction of: (a) an alkyl amido propyl hydroxysultaineand/or alkyl amido propyl betaines and/or alkyl hydroxysultaines and/oralkyl betaines; (b) an anionic surfactant, which is a mixture of (b1)alkyl hydroxy sulphonates of sodium; and (b2) alkenyl sulphonates ofsodium; (c) a cationic surfactant which is tetra-alkyl ammonium halides;and optionally, (d) copolymers derived from itaconic acid/vinylsulfonate of sodium and/or terpolymers derived from itaconic acid/sodiumvinyl sulphonate/aconitic acid.
 2. The composition according to claim 1,wherein (a) is an alkyl amidopropyl hydroxysultaine.
 3. The compositionaccording to claim 2, characterized in that the weight ratio of(a):(b1):(b2):(c) is in the range of 2:1:1:0.1 to 4:2:1:0.5.
 4. Thecomposition according to claim 1, wherein (a) is alkyl amido propylhydroxysultaines and (d) is present.
 5. The composition according toclaim 4, wherein the weight ratio of (a):(b1):(b2):(c):(d) is in therange of 2:1:1:0.1:0.01 to 4:2:1:0.5:0.2.
 6. The composition accordingto claim 1, wherein (a) is alkyl amido propyl betaines and (d) ispresent.
 7. The composition according to claim 6, wherein the weightratio of (a):(b1):(b2):(c):(d) is in the range of 1:1:1:0.1:0.01 to4:2:1:0.5:0.2.
 8. The composition according to claim 1, wherein (a) isalkyl hydroxysultaines.
 9. The composition according to claim 8, whereinthe weight ratio of (a):(b1):(b2):(c) is in the range of 2:1:1:0.1 to4:2:1:0.5.
 10. The composition according to claim 1, wherein (a) isalkyl hydroxysultaines and (d) is present.
 11. The composition accordingto claim 10, wherein the weight ratio of (a):(b1):(b2):(c):(d) is in therange of 2:1:1:0.1:0.01 to 4:2:1:0.5:0.2.
 12. The composition accordingto claim 1, wherein (a) is alkyl betaines.
 13. The composition accordingto claim 12, wherein the weight ratio (a):(b1):(b2):(c) is in the rangeof 1:1:1:0.1 to 4:2:1:0.5.
 14. The composition according to claim 1,wherein (a) is alkyl betaines and (d) is present.
 15. The compositionaccording to claim 14, wherein the weight ratio of (a):(b1):(b2):(c):(d)is in the range of 1:1:1:0.1:0.01 to 4:2:1:0.5:0.2.
 16. The compositionaccording to claim 1, wherein the alkyl amidopropyl hydroxysultaine isselected from the group consisting of ethyl amido-propylhydroxysultaine, propyl-amido-propyl hydroxysultaine, thebutyl-amido-propyl hydroxysultaine, the pentyl-amido-propylhydroxysultaine, the amido-propyl hexyl hydroxysultaine, theamido-propyl-heptyl hydroxysultaine, the octyl-amido-propylhydroxysultaine, the nonyl-amido-propyl hydroxysultaine thedecyl-amido-propyl hydroxysultaine, the undecyl-amido-propylhydroxysultaine, the dodecyl amido-propyl hydroxysultaine, thetetradecyl-amido-propyl hydroxysultaine, hexadecyl-amido-propylhydroxysultaine, octadecyl-amido-propyl hydroxysultaine, hydroxysultainecoco-amido-propyl, and mixtures thereof.
 17. The composition accordingto claim 1, wherein the alkyl amido propyl betaines are selected fromthe group consisting of ethyl amido propyl betaine, propyl-amidopropyl-betaine, butyl-amido-propyl betaine, pentyl-amido-propyl betaine,hexyl-amido-propyl betaine, amido heptyl-amido-propyl betaine,octyl-amido-propyl betaine, nonyl-amido-propyl betaine,decyl-amido-propyl betaine, un-decyl-amido-propyl betaines, dodecylamido propyl betaine, tetra decyl-amido-propyl betaine,hexadecyl-amido-propyl betaine, octa decyl-amido-propyl betaine, cocoamido propyl betaine, and mixtures thereof.
 18. The compositionaccording to claim 1, wherein the alkyl hydroxysultaines are selectedfrom the group consisting of ethyl hydroxysultaine, propylhydroxysultaine, butyl-hydroxysultaine, pentyl-hydroxysultaine, hexylhydroxysultaine, heptyl hydroxysultaine, octyl hydroxysultaine, nonylhydroxysultaine, decyl hydroxysultaine, undecyl hydroxysultaine, dodecylhydroxysultaine, tetradecyl hydroxysultaine, hexadecyl hydroxysultaine,coco-hydroxysultaine, and mixtures thereof.
 19. The compositionaccording to claim 1, wherein the alkyl betaines are selected from thegroup consisting of ethyl betaine, propyl betaine, butyl-betaine, pentylbetaine, hexyl betaine, heptyl betaine, octyl betaine, nonyl betaine,decyl betaine, undecyl betaine, dodecyl betaine, tetradecyl betaine,hexadecyl betaine, coco-betaine, and mixtures thereof.
 20. Thecomposition according to claim 1, wherein the alkyl hydroxy sulphonatesof sodium are selected from the group consisting of3-hydroxybutane-1-sulfonate of sodium, 3-hydroxypentane-1-sulfonate ofsodium, 3-hydroxyhexane-1-sulfonate of sodium,3-hidroxiheptano-1-sulfonate of sodium, 3-hidroxioctano-1-sulfonate ofsodium, 3-hidroxinonano-1-sulfonate of sodium,3-hidroxidecano-1-sulfonate, 3-hidroxiundecano-1-sulfonate of sodium,3-hidroxidodecano-1-sulfonate of sodium,3-hidroxitetradecano-1-sulfonate of sodium,3-hidroxihexadecano-1-sulfonate of sodium, 2-hydroxybutane-1-sulfonateof sodium, 2-hydroxypentane-1-sulfonate of sodium,2-hidroxihexano-1-sulfonate of sodium, 2-hidroxiheptano-1-sulfonate ofsodium, 2-hidroxioctano-1-sulfonate of sodium,2-hidroxinonano-1-sulfonate of sodium, 2-hidroxidecano-1-sulfonatesodium 2-hidroxiundecano-1-sulfonate of sodium,2-hidroxidodecano-1-sulfonate of sodium,2-hidroxitetradecano-1-sulfonate of sodium,2-hidroxihexadecano-1-sulfonate of sodium, and a mixture thereof. 21.The composition according to claim 1, wherein the alkyl sulphonates ofsodium are selected from the group consisting of but-2-en-1-sulfonate ofsodium, pent-2-en-1-sulfonate of sodium, hex-2-en-1-sulfonate of sodium,hept-2-in-1-sulfonate of sodium, oct-2-en-1-sulfonate of sodium,non-2-en-1-sulfonate of sodium, dec-2-en-1-sulfonate of sodium,undec-2-en-1-sulfonate of sodium, dodec-2-en-1-sulfonate of sodium,tetradec-2-en-1-sulfonate of sodium, hexadec-2-en-1-sulfonate of sodium,and a mixture thereof.
 22. The composition according to claim 1, whereinthe tetra-alkyl ammonium halides are selected from the group consistingof butyl trimethyl ammonium chloride, hexyl trimethyl ammonium chloride,octyl trimethyl ammonium chloride, decyl trimethyl ammonium chloride,dodecyl trimethyl ammonium chloride, trimethyl tetradecyl ammoniumchloride, hexadecyl trimethyl ammonium chloride, butyl trimethylammonium bromide, hexyl trimethyl ammonium bromide, octyl trimethylammonium bromide, decyl trimethyl ammonium bromide, dodecyl trimethylammonium bromide, tetradecyl trimethyl ammonium bromide, and hexadecyltrimethyl ammonium bromide.
 23. The composition according to claim 1,wherein the composition further comprises a zwitterionic geminal liquidselected from the group consisting of linear or branched of the typebis-N alkenyl N polyether beta amino acid, bis-N-alkyl-N-polyether-betaamino acid, and bis-N, N-dialkyl-N-polyether betaine.
 24. Thecomposition according to claim 1, wherein the average range of molecularweight for the copolymers based in itaconic acid/vinyl sulfonate ofsodium or terpolymers derived from itaconic acid/vinyl sulfonatesodium/aconitic acid is 800 to 20,000 g/mol, and wherein thepolydispersity index is 1.10 to 1.30.
 25. The composition according toclaim 1, obtained from making the mixture in aqueous solvents, alcoholsor aqueous solvent mixture and alcohols.
 26. The composition accordingto claim 25, wherein the aqueous solvents that are selected from freshwater, sea water, formation water, and/or mixtures thereof.
 27. Thecomposition according to claim 25, wherein the alcohols are selectedfrom methanol, ethanol, isopropanol, and mixtures thereof.
 28. Thecomposition according to claim 1, wherein the weight percentage of thecomposition in aqueous solvent or alcohol or aqueous solvent mixture andalcohols, are in the range of 0.5 to 99.5%.
 29. The compositionaccording to claim 1, wherein the amount of principal active componentof said composition varies from 10 to 90 Wt %.
 30. The compositionaccording to claim 1, wherein the gas used to form the foam is selectedfrom: nitrogen, oxygen, carbon dioxide, natural gas, methane, propane,butane, or mixtures of two or more of these gases.
 31. A method ofenhancing oil or gas recovery, the method comprising injecting orpumping a foam comprising the composition according to claim 1 into aformation or well comprising oil or gas.
 32. The method of claim 31,wherein the operating temperature is up to 200° C.
 33. The method ofclaim 31, wherein the operating pressure is up to 8000 psi (563 Kg/cm²).34. The method of claim 31 wherein the salinity as sodium chloride is upto 400,000 ppm.
 35. The method of claim 31, wherein the total hardnessas calcium carbonate is up to 250,000 ppm.
 36. The method of claim 31,wherein the concentration of said composition to be injected is in therange of 25 to 40,000 ppm.
 37. The method of claim 36, wherein theconcentration to be injected is from 500 to 10,000 ppm.
 38. A process ofenhanced recovery and/or production assurance of sequenced batch usingthe composition of claim 1, characterized by a) it is produced thegeneration of the foam with the first of the batch; and, b) thereafter agas is injected as a displacement fluid.
 39. The process of claim 38,wherein it is performed through an injection well and production well.40. The process of claim 38, wherein it is carried out through the samewell which acts as an injector and producer.